PROCESS FOR PREPARING HETEROAROMATIC RING COMPOUND HAVING N-Rf GROUP

ABSTRACT

There is provided a preparation process in which a N—H group of a heteroaromatic ring compound having a N—H group in its ring is converted directly to a N—Rf group at a high reaction efficiency without using a catalyst. The preparation process is a process for preparing a compound comprising a heteroaromatic ring structure having a N—Rf group (—Rf is a fluorine-containing organic group) in its ring and is characterized in that the heteroaromatic ring compound having a N—H group in its ring is allowed to react with fluoroalkene in the absence of an alkali metal.

TECHNICAL FIELD

The present invention relates to a process for preparing aheteroaromatic ring compound which is useful as a starting material fora salt of heteroaromatic ring compound usable as an ionic liquid, acuring agent such as an epoxy resin or a polyurethane resin, variousagricultural chemicals, intermediates for medicines such as antibioticsand anti-AIDS drugs and intermediates of dye, and further relates to aprocess for preparing a salt of heteroaromatic ring compound.

BACKGROUND ART

Liquid salts of imidazole compounds have ionic conductivity, flameretardance, non-volatility, high polarity and solubility, and by makinguse of these properties, are expected to be ionic liquids having variousfunctions useful for electrolytes for fuel cell, secondary battery,capacitor, dye-sensitized solar cell and electrochromic device, orreaction media, catalyst, and chemical separation and reprocessing ofnuclear fuel.

For example, JP2003-62467A discloses an ionic liquid compositioncontaining 1-(2,2,2-trifluoroethyl)-3-methylimidazoliumtrifluoromethanesulfonate. This salt of an imidazole compound isprepared by allowing 1-(methoxyethyl)-3-methylimidazoliumtrifluoromethanesulfonate to react with trifluoromethanesulfonicanhydride in the presence of trifluoroethanol and pyridine as disclosedin P. Bonhote et al., Inorganic Chemistry, 35, pp. 1168-1178 (1996).However in this preparation process, separation of impurities derivedfrom unreacted imidazolium salt is difficult, and in addition, anexpensive reacting agent is used and yield is as low as about 28%. Alsoin the structure of this imidazolium salt, a fluorine-containing alkylgroup is not introduced directly on nitrogen, and an effect ofincreasing cations for use as a Lewis acid catalyst is difficult toobtain.

V. V. Rudyuk et al., J. Fluorine Chem., 125, pp. 1465-1471 (2004)discloses that after conversion of an imidazole compound into apotassium salt, when the potassium salt is allowed to react withCF₂═CFCl under refluxing in dimethylacetamide, an imidazole compound inwhich N—K groups of the imidazole compound have been converted toN—CF═CFCl groups and N—CF₂CFCl groups can be obtained, and yield of theimidazole compound having N—CF₂CFCl groups is 20 to 85%, and alsodiscloses that when an imidazole compound is allowed to react directlywith CF₂═CF₂ in tetrahydrofuran in the presence of a catalytic amount ofmetallic potassium, an imidazole compound in which N—H groups of theimidazole compound have been converted to N—CF₂CFH groups can beobtained at yield of 68%.

D. C. England et al., J. Am. Chem. Soc., 82, pp. 5116-5122 (1960) andU.S. Pat. No. 2,861,990 disclose that a pyrrole compound or an indolecompound is allowed to react with fluoroalkene such as CF₂═CF₂, CF₂═CFClor CF₂═CFCF₃ in the presence of metallic potassium or metallic sodium,and a pyrrole compound or an indole compound in which a N—H group of thepyrrole compound or the indole compound has been added to thefluoroalkene can be obtained at yield of 60 to 88%.

Alkali metals described in these V. V. Rudyuk et al., J. Fluorine Chem.,125, pp. 1465-1471 (2004), D. C. England et al., J. Am. Chem. Soc., 82,pp. 5116-5122 (1960) and U.S. Pat. No. 2,861,990 are substances whichare so easily reactable with water, and handling thereof is not easybecause water control of all chemicals to be used in the reaction andwater control in working environment are necessary. In addition, inthese processes, a step for removing alkali metal salt produced afterthe reaction is required.

Further, for ionization of an obtained imidazole compound having afluoroalkyl group, there is employed a method of anion exchange bysubstitution reaction of the compound with methyl iodide as disclosed inY. L. Yagupolskii et al., J. Fluorine Chem., 126, pp. 669-672 (2005).

DISCLOSURE OF INVENTION

The present inventors have studied a process for preparing an imidazolecompound having a fluorine-containing group at high yield, and as aresult, unexpectedly have found that by subjecting an imidazole compoundin a molten state to reaction in the absence of a solvent, an imidazolecompound having a fluorine-containing group can be prepared at highyield even without forming the imidazole compound into an alkali metalsalt or using a catalytic amount of alkali metal. The present inventorshave made further investigations based on this finding, and havecompleted the present invention.

Namely, the present invention relates to a process (the firstpreparation process) for preparing a compound (C) comprising aheteroaromatic ring structure having a N—Rf group in its ring, which ischaracterized in that a heteroaromatic ring compound (A) having a N—Hgroup in its ring is allowed to react, in the absence of alkali metal,with a fluoroalkene (B) represented by the formula (B):

wherein R^(b1), R^(b2) and R^(b3) are the same or different and each isH, halogen atom, a functional group or a monovalent organic group whichmay be substituted by halogen atom, may have an ether bond and may havea polymerizable group, and—Rf is represented by the formula (c):

wherein R^(c1) is the same as R^(b1) of the formula (B); R^(c2) is thesame as R^(b2) of the formula (B); R^(c3) is the same as R^(b3) of theformula (B).

Also the present invention relates to a process (the second preparationprocess) for preparing a salt (E) comprising a heteroaromatic ringstructure having a N—Rf group in its ring, which is characterized inthat subsequently to the above-mentioned preparation process, a saltforming compound (D) is acted on the obtained compound (C) comprising aheteroaromatic ring structure having a N—Rf group in its ring and ifnecessary, anion exchanging is further carried out.

The present invention further relates to a novel compound (C1)comprising a heteroaromatic ring structure having a N—Rf group in itsring and a novel salt (E1) comprising a heteroaromatic ring structurehaving a N—Rf group in its ring.

BEST MODE FOR CARRYING OUT THE INVENTION

The first preparation process of the present invention is a process forpreparing the compound (C) comprising a heteroaromatic ring structurehaving a N—Rf group in its ring, which is characterized in that theheteroaromatic ring compound (A) having a N—H group in its ring isallowed to react, in the absence of alkali metal, with the fluoroalkene(B) represented by the above-mentioned formula (B).

Examples of the heteroaromatic ring compound (A) having a N—H group inits ring which is a starting material are heteroaromatic ring compounds(A1) represented by the formula (A1):

wherein

is a moiety forming a heteroaromatic ring together with a nitrogen atomand the whole or a part of its hydrogen atoms may be substituted by thesame or different organic groups.

Among such compounds, a compound having an imidazole skeleton, a pyrroleskeleton, a pyrazole skeleton, a triazole skeleton, an indole skeleton,a purine skeleton or a purine derivative is preferable from theviewpoint of easy synthesis and availability.

Especially examples of the heteroaromatic ring compound (A1) representedby the above-mentioned formula (A1) are an imidazole compoundrepresented by the formula (A1-1):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them,a pyrrole compound represented by the formula (A1-2):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them,a pyrazole compound represented by the formula (A1-3):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them,a triazole compound represented by the formula (A1-4):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them,an indole compound represented by the formula (A1-5):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring and/or the aromatic ring aresubstituted by them,a purine compound represented by the formula (A1-6):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring and/or the aromatic ring aresubstituted by them, anda purine derivative represented by the formula (A1-7):

wherein R^(a) is halogen atom, a functional group or an organic groupand may be present or may not be present, and when R^(a) is present, thewhole or a part of hydrogen atoms of the heteroaromatic ring aresubstituted by R^(a); R and R′ are the same or different and each ishydrogen atom, an alkyl group, an arylalkyl group, an organosilicongroup, an alkoxyl group or a carboxyester group; Ys are the same ordifferent and each is ═O, —NRR′, —OR, F or F₂,and compounds explained infra.

Examples of R^(a) are, for instance, groups raised below.

(a1-1) Halogen Atoms:

There are preferably fluorine atom and chlorine atom, especiallyfluorine atom.

(a1-2) Functional Groups:

Examples are carboxyl group (—COOH), carboxylic acid ester group(—COOR), nitrile group (—CN), amino group (—NH₂), alkylamino group(—NR₂, —NHR), carboxamide group (—CONR₂, —CONHR), alkyl ether group(—OR), silyl ether group (—OSiR₃), thiol group (—SH), thioether group(—SR) and nitro group, preferably carboxylic acid ester group, nitrilegroup, amino group, alkylamino group, carboxamide group, alkyl ethergroup, silyl ether group, thiol group and thioether group. In addition,carboxyl group (—COOH), carboxylic acid ester group (—COOR), nitrilegroup (—CN), amino group (—NH₂), alkylamino group (—NR₂, —NHR),carboxamide group (—CONR₂, —CONHR), alkyl ether group (—OR), silyl ethergroup (—OSiR₃), thiol group (—SH), thioether group (—SR) and nitro groupare allowable as a substituent group to be bonded to the benzene ring(Rs are the same or different, and are preferably monovalent hydrocarbongroups).

(a1-3) Organic Groups:(a1-3-1) Linear or branched alkyl groups in which a part or the whole ofhydrogen atoms may be substituted by halogen atoms, preferably fluorineatoms. The number of carbon atoms is preferably 1 to 1,000.(a1-3-2) Alkyl groups substituted by functional group such as carboxylgroup, hydroxyl group, nitrile group, amino group, alkylamino group,carboxylic acid ester group, carboxamide group, alkyl ether group, silylether group, thiol group, thioether group or nitro group. The number ofcarbon atoms is preferably 1 to 20.(a1-3-3) Aryl groups which may be substituted.(a1-3-4) Alkyl groups having ether bond in which a part or the whole ofhydrogen atoms may be substituted by halogen atoms, preferably fluorineatoms. The number of carbon atoms is preferably 1 to 1,000.(a1-3-5) Alkoxyl groups in which a part or the whole of hydrogen atomsmay be substituted by halogen atoms, preferably fluorine atoms. Thenumber of carbon atoms is preferably 1 to 1,000.

In the following Tables 1 to 13, definitions of substituents areeffective only in the corresponding tables. Figures showing the numberof atoms are not represented especially by small letters. Further Ph, iand n are abbreviations of phenyl, iso and normal, respectively.

Examples of the imidazole compounds of the formula (A1-1) are, forinstance, compounds having R^(a1) shown in Table 1.

TABLE 1

Compound No. R^(a1) A1-1-1 H H H  2 F H H  3 F F H  4 F F F  5 CF3 H H 6 CF3 F H  7 C2F5 H H  8 iC3F7 H H  9 C4H9 H H 10 CHF2CF2 H H 11CF3CHFCF2 H H 12 CH3 H H 13 CH3 F H 14 CH3 CH3 H 15 Ph H H 16 Ph F H 17CH3 Ph H 18 C2H5 H H 19 nC3H7 H H 20 iC3H7 H H 21 nC4H9 H H 22 CH2OR H H23 COOR H H 24 COOR F H 25 Cl H H 26 C4H9 CH2OR Cl 27 CH2CH(NRR′)COOR HH 28 CH2CH(NRR′)COOR F H 29 CH2CN H H 30 CH2CN F H 31 CH2COOH H H 32CH2COOH F H

Examples of the pyrrole compounds of the formula (A1-2) are, forinstance, compounds having R^(a2) shown in Table 2.

TABLE 2

Compound No. R^(a2) A1-2-1 H H H H  2 F H H H  3 F F H H  4 F F F H  5 FF F F  6 CF3 H H H  7 CF3 F H H  8 CF3 F F H  9 C2F5 H H H 10 iC3F7 H HH 11 C4F9 H H H 12 CH3 H H H 13 CH3 F H H 14 CH3 CH3 H H 15 Ph H H H 16Ph F H H 17 CH3 Ph H H 18 C2H5 H H H 19 nC3H7 H H H 20 iC3H7 H H H 21nC4H9 H H H 22 CH2OR H H H 23 COOR H H H 24 COOR F H H 25 Cl H H H 26CH(NRR′)COOR H H H 27 CH(NRR′)COOR F H H 28 CH2CH2NRR′ H H H 29CH2CH2NRR′ F H H 30 CH2CN H H H 31 CH2CN F H H 32 CH2COOH H H H 33CH2COOH F H H

Examples of the pyrazole compounds of the formula (A 1-3) are, forinstance, compounds having R^(a3) shown in Table 3.

TABLE 3

Compound No. R^(a3) A1-3-1 H H H  2 F H H  3 F F H  4 F F F  5 CF3 H H 6 CF3 F H  7 C2F5 H H  8 iC3F7 H H  9 C4F9 H H 10 CHF2CF2 H H 11CF3CHFCF2 H H 12 CH3 H H 13 CH3 F H 14 CH3 CH3 H 15 Ph H H 16 Ph F H 17CH3 Ph H 18 C2H5 H H 19 nC3H7 H H 20 iC3H7 H H 21 nC4H9 H H 22 CH2OR H H23 COOR H H 24 COOR F H 25 Cl H H

Examples of the triazole compounds of the formula (A1-4) are, forinstance, 1,2,4-triazole compounds having R^(a4) shown in Table 4.

TABLE 4

Compound No. R^(a4) A1-4-1 H H  2 F H  3 F F  4 CF3 H  5 CF3 F  6 C2F5 H 7 iC3F7 H  8 C4F9 H  9 CHF2CF2 H 10 CF3CHFCF2 H 11 CH3 H 12 CH3 F 13CH3 CH3 14 Ph H 15 Ph F 16 CH3 Ph 17 C2H5 H 18 nC3H7 H 19 iC3H7 H 20nC4H9 H 21 CH2OR H 22 COOR H 23 COOR F 24 Cl H 25 Cl F

Examples of the indole compounds of the formula (A1-5) are, forinstance, compounds having R^(a5) and R^(a6) shown in Table 5.

TABLE 5

Compound No. R^(a6) R^(a5) A1-5-1 H H H H H H  2 F H H H H H  3 F F H HH H  4 H H H H F H  5 F H H H F H  6 H H H H CH3 H  7 F H H H CH3 H  8COOR H H H H H  9 COOR F H H H H 10 H H H H COOR H 11 F H H H COOR H 12H H H H CH(NRR′)COOR H 13 F H H H CH(NRR′)COOR H 14 H H H H CH2NRR′ H 15F H H H CH2NRR′ H 16 H H H H CN H 17 F H H H CN H

Examples of the purine compounds of the formula (A1-6) are, forinstance, compounds having R^(a7) and R^(a8) shown in Table 6.

TABLE 6

Compound No. R^(a8) R^(a7) A1-6-1 H H H  2 F H H  3 F F H  4 H H F  5 FH F  6 H H CF3  7 F H CF3  8 H H CH3  9 F H CH3 10 COOR H H 11 COOR F H12 CH3 H H 13 CH3 F H 14 Ph H H 15 Ph F H 16 CH3 H H 17 CH3 F H 18 NR2 HH 19 NR2 F H 20 OR H H 21 OR F H

Examples of the purine derivatives of the formula (A1-7) are, forinstance, compounds having R^(a9) and R^(a10) shown in Table 7.

TABLE 7

Compound No. Y R^(a9) A1-7-1 ═O ═O H  2 ═O ═O CH3  3 ═O ═O Ph  4 ═O ═OOR  5 ═O ═O F  6 ═O NRR′ H  7 ═O NRR′ CH3  8 ═O OR H  9 ═O OR CH3 10 ═OF H 11 ═O F CH3 12 ═O F2 H 13 ═O F2 CH3 14 ═O F2 Ph 15 ═O F2 OR 16 ═O F2F R or R′ = H, CH3, Si(CH3)3, Si(CH3)2tBu, Si(iPr)3, SiEt3, CH2Ph,C(Ph)3, CH3CO, COOMe, COOtBu

Examples of other heteroaromatic ring compounds (A) are, for instance,benzimidazole compounds shown in Table 8, 1,2,3-triazole compounds shownin Table 9, tetrazole compounds shown in Table 10, isoindole compoundsshown in Table 11, indazole compounds shown in Table 12 andbenzotriazole compounds shown in Table 13.

TABLE 8

Compound No. R^(a11) R^(a10) A1-8-1 H H H H H  2 F H H H H  3 F F H H H 4 H H H H F  5 F H H H F  6 H H H H CF3  7 F H H H CF3  8 H H H H CH3 9 F H H H CH3 10 F F H H CH3 11 COOR H H H H 12 COOR F H H H 13 CH3 H HH H 14 CH3 F H H H 15 Ph H H H H 16 Ph F H H H 17 CH3 H H H H 18 CH3 F HH H 19 H H H H COOR 20 F H H H COOR 21 F F H H COOR 22 H H H H CN 23 F HH H CN 24 F F H H CN

TABLE 9

Compound No. R^(a10) A1-9-1 H H  2 F H  3 F F  4 CF3 H  5 CF3 F  6 C2F5H  7 iC3F7 H  8 C4F9 H  9 CHF2CF2 H 10 CF3CHFCF2 H 11 CH3 H 12 CH3 F 13CH3 CH3 14 Ph H 15 Ph F 16 CH3 Ph 17 C2H5 H 18 nC3H7 H 19 iC3H7 H 20nC4H9 H 21 CH2OR H 22 COOR H 23 COOR F 24 Cl H 25 Cl F

TABLE 10

Compound No. R^(a10) A1-10-1 H  2 F  3 CF3  4 C2F5  5 iC3F7  6 C4F9  7CHF2CF2  8 CF3CHFCF2  9 CH3 10 Ph 11 C2H5 12 nC3H7 13 iC3H7 14 nC4H9 15CH2OR 16 COOR 17 Cl

TABLE 11

Compound No. R^(a11) R^(a10) A1-11-1 H H H H H H  2 F H H H H H  3 F F HH H H  4 H H H H F H  5 F H H H F H  6 H H H H CH3 H  7 F H H H CH3 H  8COOR H H H H H  9 COOR F H H H H 10 H H H H COOR H 11 F H H H COOR H 12H H H H CH(NRR′)COOR H 13 F H H H CH(NRR′)COOR H 14 H H H H CH2NRR′ H 15F H H H CH2NRR′ H 16 H H H H CN H 17 F H H H CN H

TABLE 12

Compound No. R^(a11) R^(a10) A1-12-1 H H H H H  2 F H H H H  3 F F H H H 4 H H H H F  5 F H H H F  6 H H H H CF3  7 F H H H CF3  8 H H H H CH3 9 F H H H CH3 10 F F H H CH3 11 COOR H H H H 12 COOR F H H H 13 CH3 H HH H 14 CH3 F H H H 15 Ph H H H H 16 Ph F H H H 17 CH3 H H H H 18 CH3 F HH H 19 H H H H COOR 20 F H H H COOR 21 F F H H COOR 22 H H H H CN 23 F HH H CN 24 F F H H CN

TABLE 13

Compound No. R^(a11) A1-13-1 H H H H  2 F H H H  3 F F H H  4 F F F H  5F F F F  6 COOR H H H  7 COOR F H H  8 CH3 H H H  9 CH3 F H H 10 Ph H HH 11 Ph F H H 12 OR H H H 13 OR F H H

The fluoroalkene (B) which is allowed to react with the heteroaromaticring compound (A) and is represented by the formula (B):

wherein R^(b1), R^(b2) and R^(b3) are the same or different and each isH, halogen atom, a functional group or a monovalent organic group whichmay be substituted by halogen atom, may have an ether bond and may havea polymerizable group, is one being capable of undergoing additionreaction with the N—H group of the heteroaromatic ring compound (A).

It is preferable that at least one of R^(b1), R^(b2) and R^(b3),especially at least either R^(b1) or R^(b2) has the formula (b-1):

—(CF₂)_(m1)—

wherein m1 is an integer of 1 to 10,000,the formula (b-2):

wherein m2 is an integer of 1 to 10,000,the formula (b-3):

—(CF₂—CH₂)_(m3)—

wherein m3 is an integer of 1 to 10,000,the formula (b-4):

wherein m4 is an integer of 1 to 3,000, and/orthe formula (b-5):

—(Rf^(b)O)_(m5)—

wherein Rf^(b) is a linear or branched alkylene group having fluorineatom; m5 is an integer of 1 to 100. Especially preferable is one havingthe perfluoroalkylene group of the formula (b-4) having a branched chainand/or the fluoroether unit of the formula (b-5) since a liquid state iseasily exhibited at room temperature.

In addition, the end of at least one of R^(b1), R^(b2) and R^(b3) may bea polymerizable group (b-6). Examples of the polymerizable group are,for instance, a carbon-carbon double bond, a hydroxyl group, a carboxylgroup, an amino group, an isocyanate group, a thiol group and athioisocyanate group, especially preferably a carbon-carbon double bond.

From a different point of view, preferable examples of R^(b1), R^(b2)and R^(b3) are those raised below.

(b1-1) Hydrogen Atom(b1-2) Halogen Atoms:

There are chlorine atom, fluorine atom, and bromine atom, and fluorineatom is especially preferable.

(b1-3) Functional Groups:

There are preferably a carboxyl group (—COOH), a carboxylic acid estergroup (—COOR), a nitrile group (—CN) and an amino group.

(b1-4) Organic Groups:(b1-4-1) Linear or branched alkyl groups, in which a part or the wholeof hydrogen atoms may be substituted by halogen atoms, preferablyfluorine atoms.(b1-4-2) Alkyl groups having functional group such as carboxyl group,hydroxyl group, nitrile group or amino group.(b1-4-3) Aryl groups which may be substituted.(b1-4-4) Alkyl groups having an ether bond, in which a part or the wholeof hydrogen atoms may be substituted by halogen atoms, preferablyfluorine atoms.(b1-4-5) Alkoxyl groups, in which a part or the whole of hydrogen atomsmay be substituted by halogen atoms, preferably fluorine atoms.

Preferable examples of the fluoroalkene (B) are, for instance,fluorine-containing olefins such as CF₂═CF₂, CF₂═CF(CF₃), CF₂═C(CF₃)₂,CF₂═C(CF₃)Br, CF₂═C(CF₃)Cl, CF₂═C(CF₃)I, CF₂═CFBr, CF₂═CFCl, CF₂═CFI,(CF₃)₂CFCF₂CF═CF₂, (CF₃)₂CFCF═CFCF₃, (CF₃)₂C═CFCF₂CF₃, CF₂═CH₂, CF₂═CFH,CF₂═CF(Rf^(B))_(n)CF═CH₂ (Rf^(B) is CF₂CF₂, CF₂CFCl, CF₂CF(CF₃) orCF₂CH₂; n is 0 or an integer of 1 to 1,000), CF₂═CF(Rf^(B))_(n)—CF═CF₂(Rf^(B) is CF₂CF₂, CF₂CFCl, CF₂CF(CF₃) or CF₂CH₂; n is 0 or an integerof 1 to 1,000), CF₂═CH(Rf^(B))_(n)—CH═CF₂ (Rf^(B) is CF₂CF₂, CF₂CFCl,CF₂CF(CF₃) or CF₂CH₂; n is 0 or an integer of 1 to 1,000),CF₂═CH(Rf^(B))_(n)—CF═CF₂ (Rf^(B) is CF₂CF₂, CF₂CFCl, CF₂CF(CF₃) orCF₂CH₂; n is 0 or an integer of 1 to 1,000), CF₂═CF(Rf^(B))_(n)—F(Rf^(B) is CF₂CF₂, CF₂CFCl, CF₂CF(CF₃) or CF₂CH₂; n is 0 or an integerof 1 to 1,000), CF₂═CH(Rf^(B))_(n)—F (Rf^(B) is CF₂CF₂, CF₂CFCl,CF₂CF(CF₃) or CF₂CH₂; n is 0 or an integer of 1 to 1,000),CF₂═CF(Rf^(B))_(n)—Br (Rf^(B) is CF₂CF₂, CF₂CFCl, CF₂CF(CF₃) or CF₂CH₂;n is 0 or an integer of 1 to 1,000), CF₂═CH(Rf^(B))_(n)—Br (Rf^(B) isCF₂CF₂, CF₂CFCl, CF₂CF(CF₃) or CF₂CH₂; n is 0 or an integer of 1 to1,000), CF₂═CF(Rf^(B))_(n)—Cl (Rf^(B) is CF₂CF₂, CF₂CFCl, CF₂CF(CF₃) orCF₂CH₂; n is 0 or an integer of 1 to 1,000), CF₂═CH(Rf^(B))_(n)—Cl(Rf^(B) is CF₂CF₂, CF₂CFCl, CF₂CF(CF₃) or CF₂CH₂; n is 0 or an integerof 1 to 1,000), CF₂═CF(Rf^(B))_(n)—I (Rf^(B) is CF₂CF₂, CF₂CFCl,CF₂CF(CF₃) or CF₂CH₂; n is 0 or an integer of 1 to 1,000) andCF₂═CH(Rf^(B))_(n)—I (Rf^(B) is CF₂CF₂, CF₂CFCl, CF₂CF(CF₃) or CF₂CH₂; nis 0 or an integer of 1 to 1,000); fluorine-containing vinyl ethers suchas CF₂═CFOR (R is an alkyl group which may be substituted by halogenatom), CF₂═C(CF₃)OR (R is an alkyl group which may be substituted byhalogen atom), (CF₃)₂C═CFOR (R is an alkyl group which may besubstituted by halogen atom), CF₂═CF[OCF₂CF(CF₃)]_(n)OC₃F₇ (n is 0 or aninteger of 1 to 20), CF₂═CF[OCF₂CF(CF₃)]_(n)OCF₂CF═CF₂ (n is 0 or aninteger of 1 to 20), CF₂═CF[OCF₂CF(CF₃)]_(n)OCF₂CFClCF₂Cl (n is 0 or aninteger of 1 to 20), CF₂═CF[OCF₂CF(CF₃)]_(n)OCF₂CF₂CF═CF₂ (n is 0 or aninteger of 1 to 20), CF₂═CF[OCF₂CF(CF₃)]_(n)OCF₂CF₂CF═CH₂ (n is 0 or aninteger of 1 to 20), CF₂═CF[OCF₂CF(CF₃)]_(n)OCF₂CF₂SO₃M (M is Li, Na, K,Rb, Cs, BeCl, MgCl, MgBr, MgI, MgNO₃, MgBF₄, MgPF₆, CaCl, CaBr, Cal,CaNO₃, CaBF₄, CaPF₆, FeCl₂, FeBr₂, FeI₂, CoCl, CoBr, CoI, ZnCl, ZnBr,ZnI, NiCl, NiBr, NiI, Ag, Cu, CuCl, CuBr, CuI, AuCl₂, AuBr₂ or AuI₂; nis 0 or an integer of 1 to 20), CF₂═CF[OCF₂CF(CF₃)]_(n)O(CF₂)_(m)CO₂R (mis an integer of 1 to 10; n is 0 or an integer of 1 to 20; R is an alkylgroup which may be substituted by hydrogen atom or halogen atom),CF₂═CF[OCF₂CF(CF₃)]_(n)O(CF₂)_(m)CH₂OR (m is an integer of 1 to 10; n is0 or an integer of 1 to 20; R is hydrogen atom or an alkyl group whichmay be substituted by hydrogen atom or halogen atom) andCF₂═CF[OCF₂CF(CF₃)]_(n)O(CF₂)_(m)—I (m is an integer of 1 to 10; n is 0or an integer of 1 to 20); fluorine-containing unsaturated carboxylicacids or esters thereof such as CF₂═CY(CX₂)_(n)COOR (X is H or F; Y isH, F or CF₃; n is 0 or an integer of 1 to 20; R is an alkyl group whichmay be substituted by hydrogen atom or halogen atom);fluorine-containing unsaturated sulfonates such as CF₂═CF(CX₂)_(n)CH₂OR(X is H or F; n is 0 or an integer of 1 to 20; R is hydrogen atom or analkyl group which may be substituted by hydrogen atom or halogen atom),CF₂═CY—C₆X₄—CO₂R (X is H or F; Y is H, F or CF₃; R is an alkyl groupwhich may be substituted by hydrogen atom or halogen atom) andCF₂═CY—C₆X₄—SO₃M (X is H or F; Y is H, F or CF₃; M is Li, Na, K, Rb, Cs,BeCl, MgCl, MgBr, MgI, MgNO₃, MgBF₄, MgPF₆, CaCl, CaBr, CaI, CaNO₃,CaBF₄, CaPF₆, FeCl₂, FeBr₂, FeI₂, CoCl, CoBr, CoI, ZnCl, ZnBr, ZnI,NiCl, NiBr, NiI, Ag, Cu, CuCl, CuBr, CuI, AuCl₂, AuBr₂ or AuI₂), andCF₂═CY—C₆X₄—CH₂OR (X is H or F; Y is H, F or CF₃; R is hydrogen atom oran alkyl group which may be substituted by hydrogen atom or halogenatom).

In the first preparation process of the present invention, theheteroaromatic ring compound (A) having a N—H group is allowed to reactwith the fluoroalkene (B) in the absence of alkali metal.

The first preparation process differs from the preparation processes ofsubjecting a heteroaromatic ring compound to reaction in the form of analkali metal salt which are disclosed in V. V. Rudyuk et al., J.Fluorine Chem., 125, pp. 1465-1471 (2004), D. C. England et al., J. Am.Chem. Soc., 82, pp. 5116-5122 (1960) and U.S. Pat. No. 2,861,990 becausein the present invention, the heteroaromatic ring compound (A) having aN—H group is subjected to reaction, and also differs from the reactionsdisclosed in V. V. Rudyuk et al., J. Fluorine Chem., 125, pp. 1465-1471(2004), D. C. England et al., J. Am. Chem. Soc., 82, pp. 5116-5122(1960) and U.S. Pat. No. 2,861,990 because in the present invention,even in the case of using the heteroaromatic ring compound (A) having aN—H group as a starting material, reaction is carried out in the absenceof alkali metal.

In the preparation process of the present invention, a metal which isnot allowed to be present in a reaction system is alkali metal, and alsopresence of other metal being capable of taking part in the reactiondirectly or as a catalyst is not necessary. Also it is not especiallynecessary to allow a metal to be present even in the form of a salt or acomplex.

The reaction may be carried out in a solution of the heteroaromatic ringcompound (A) or in a molten state of the heteroaromatic ring compound(A).

When the reaction is carried out in the solution, it proceeds evenwithout using a catalyst by making the heteroaromatic ring compound (A)in a homogeneous liquid state.

Examples of a usable reaction solvent are, for instance, diethyl ether,t-butyl methyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran,dioxane, dimethoxymethane, dimethoxyethane, diglyme, triglyme,tetraglyme, N,N-dimethylformamide, N,N-dimethylacetamide,N-methylpyrrolidone, ethyl acetate, methyl acetate, propyl acetate,butyl acetate, dimethyl sulfoxide, sulfolane, hexamethylphosphorictriamide, benzene, toluene, xylene, chloroform, methylene chloride,dichloroethane, trichloroethane, dichloropentafluoropropane,dichlorofluoroethane, trichlorotrifluoroethane,tetrachlorohexafluorobutane, dichlorooctafluorobutane,pentachloropentafluorohexane, dibromotetrafluoroethane, perfluorohexane,perfluoro(butyltetrahydrofuran) and perfluorotributylamine. From theviewpoint of solubility of the heteroaromatic ring compound, preferableare diethyl ether, t-butyl methyl ether, dibutyl ether, diisopropylether, tetrahydrofuran, dioxane, dimethoxyethane, diglyme, triglyme,tetraglyme, N,N-dimethylformamide, N,N-dimethylacetamide,N-methylpyrrolidone, ethyl acetate, methyl acetate, propyl acetate,butyl acetate, dimethyl sulfoxide and sulfolane.

A concentration of the solution may be optionally selected depending onkind of the heteroaromatic ring compound, kind of a solvent, kind of thefluoroalkene and a reaction temperature. As far as a part thereof ishomogeneously dissolved, a higher concentration is preferable. Theconcentration is preferably not less than 30% by mass, furtherpreferably not less than 60% by mass.

A reaction pressure is not limited particularly. The reaction proceedsat any pressure as far as the fluoroalkene can contact with the solutioncontaining the heteroaromatic ring compound.

In the present invention, it is especially preferable that the reactionis conducted in the absence of a solvent with the heteroaromatic ringcompound (A) being in a molten state, from the viewpoint that nooperation for separating a solvent is necessary and production cost isdecreased.

In the present invention, the molten state of the heteroaromatic ringcompound encompasses not only a molten state of the heteroaromatic ringcompound alone but also a molten state of the heteroaromatic ringcompound alone at a temperature less than its melting point by blendinga melting point depressor.

Examples of a melting point depressor are the above-mentioned reactionsolvents which are used in an amount being capable of dissolving orswelling the heteroaromatic ring compound.

In the case where the reaction is conducted in a molten state, thereaction temperature is a melting point of the heteroaromatic ringcompound (A) (or a reduced melting point) or more and less than itsdecomposition temperature.

The reaction pressure is not limited particularly. The reaction proceedsat any pressure as far as the fluoroalkene can contact with the moltensubstance containing the heteroaromatic ring compound.

A method of introducing the fluoroalkene (B) to a reaction system is notlimited particularly. For example, there can be preferably employed amethod of introducing gasified fluoroalkene under pressure to thesolution of the heteroaromatic ring compound (A) or to theheteroaromatic ring compound (A) in a molten state, or a method ofadding dropwise fluoroalkene to the solution of the heteroaromatic ringcompound (A) or to the heteroaromatic ring compound (A) in a moltenstate.

The heteroaromatic ring compound (C) having a N—Rf group in its ringwhich is obtained in the first preparation process is a compoundobtained by adding the fluoroalkene (B) to the N—H group of theheteroaromatic ring compound (A) having a N—H group in its ring. Thiscompound is a fluorine-containing heteroaromatic ring compoundrepresented by the formula (C1):

wherein

is as defined in the formula (A1); Rf is as defined in the formula (c).

Accordingly, the above-mentioned fluorine-containing heteroaromatic ringcompound (C) is a compound obtained by converting the N—H group of theheteroaromatic ring compound (A) to the N—Rf group. For example, acompound having an imidazole skeleton having N—H group in its ring, acompound having a pyrrole skeleton having N—H group in its ring, acompound having a pyrazole skeleton having N—H group in its ring, acompound having a triazole skeleton having N—H group in its ring, acompound having an indole skeleton having N—H group in its ring, acompound having a purine skeleton having N—H group in its ring and apurine derivative having N—H group in its ring are formed into acompound having an imidazole skeleton having N—Rf group in its ring, acompound having a pyrrole skeleton having N—Rf group in its ring, acompound having a pyrazole skeleton having N—Rf group in its ring, acompound having a triazole skeleton having N—Rf group in its ring, acompound having an indole skeleton having N—Rf group in its ring, acompound having a purine skeleton having N—Rf group in its ring and apurine derivative having N—Rf group in its ring, respectively.

Examples of the heteroaromatic ring compound (C1) represented by theabove-mentioned formula (C1) are a fluorine-containing imidazolecompound represented by the formula (C1-1):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf is Rf¹where Rf¹ is the same as the formula (c) or is a monovalent organicgroup which may have at least one residue defined by deleting Rf groupfrom the formula (C1-1),a fluorine-containing pyrrole compound represented by the formula(C1-2):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf is Rf²where Rf² is the same as the formula (c) or is a monovalent organicgroup which may have at least one residue defined by deleting Rf groupfrom the formula (C1-2),a fluorine-containing pyrazole compound represented by the formula(C1-3):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf is Rf³where Rf³ is the same as the formula (c) or is a monovalent organicgroup which may have at least one residue defined by deleting Rf groupfrom the formula (C1-3),a fluorine-containing triazole compound represented by the formula(C1-4):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf is Rf⁴where Rf⁴ is the same as the formula (c) or is a monovalent organicgroup which may have at least one residue defined by deleting Rf groupfrom the formula (C1-4),a fluorine-containing indole compound represented by the formula (C1-5):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring and/or the aromatic ring aresubstituted by them; Rf is Rf⁵ where Rf⁵ is the same as the formula (c)or is a monovalent organic group which may have at least one residuedefined by deleting Rf group from the formula (C1-5),a fluorine-containing purine compound represented by the formula (C1-6):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring and/or the aromatic ring aresubstituted by them; Rf is Rf⁶ where Rf⁶ is the same as the formula (c)or is a monovalent organic group which may have at least one residuedefined by deleting Rf group from the formula (C1-6), anda fluorine-containing purine derivative represented by the formula(C1-7):

wherein R^(a) is halogen atom, a functional group or an organic groupand may be present or may not be present; Ys are the same or differentand each is ═O, —NRR′, —OR, F or F₂; R and R′ are the same or differentand each is hydrogen atom, an alkyl group, an arylalkyl group, anorganosilicon group, an alkoxyl group or a carboxyester group; Rf is Rf⁷where Rf⁷ is the same as the formula (c) or is a monovalent organicgroup which may have at least one residue defined by deleting Rf groupfrom the formula (C1-7),and examples of the substituent groups thereof are those concretelyexemplified in the heteroaromatic ring compound (A1) and thefluoroalkene (B).

Examples of the heteroaromatic ring compound (C) having N—Rf group inits ring are fluorine-containing imidazole compounds shown in Table 14,fluorine-containing pyrrole compounds shown in Table 15,fluorine-containing pyrazole compounds shown in Table 16,fluorine-containing triazole compounds shown in Table 17,fluorine-containing indole compounds shown in Table 18,fluorine-containing purine compounds shown in Table 19,fluorine-containing purine derivatives shown in Table 20,fluorine-containing benzimidazole compounds shown in Table 21,fluorine-containing 1,2,3-triazole compounds shown in Table 22,fluorine-containing tetrazole compounds shown in Table 23,fluorine-containing isoindole compounds shown in Table 24,fluorine-containing indazole compounds shown in Table 25, andfluorine-containing benzotriazole compounds shown in Table 26.

In the following Tables 14 to 26, definitions of each substituent areeffective only in the corresponding tables. Figures showing the numberof atoms are not represented especially by small letters. Further Ph, iand n are abbreviations of phenyl, iso and normal, respectively.

TABLE 14

Compound No. R^(a1) Rb1 Rb2 Rb3 C1-1-1 H H H F F F  2 H H H F CF3 F  3 HH H F OCF3 F  4 H H H H H F  5 H H H CF3 CF3 F  6 H H H CF3 CF3 OCH3  7H H H COOR F F  8 H H H COOR CF3 F  9 H H H CF2COOR F F 10 H H HCF2CH2OR F F 11 H H H CF2CF(CF3)2 F F 12 H H H F CF(CF3)2 CF3 13 H H HCF3 F CF(CF3)2 14 H H H OAlkyl F F 15 H H H F [OCF2CF(CF3)]nOC3F7 F 16 HH H F [OCF2CF(CF3)]nOCF2CF═CH2 F 17 H H H F [OCF2CF(CF3)]nOCF2CFClCF2ClF 18 H H H F [OCF2CF(CF3)]nO(CF2)mCFClCF2Cl F 19 H H H F[OCF2CF(CF3)]nO(CF2)m] F 20 H H H F [OCF2CF(CF3)]nOCF2CF2SO2R F 21 H H HF [OCF2CF2]nO(CF2)mCFClCF2Cl F 22 H H H F [OCF2CF2]nO(CF2)mF F 23 H H HH (CF2)nF F 24 H H H H (CF2)nI F 25 H H H F Cl F 26 CH3 H H F F F 27 CH3H H F CF3 F 28 CH3 CH3 H F F F 29 CH3 CH3 H F CF3 F 30 Ph H H F F F 31Ph H H F CF3 F 32 CH3 Ph H F F F 33 CH3 Ph H F CF3 F 34 CH2OR H H F F F35 CH2OR H H F CF3 F 36 COOR H H F F F 37 COOR H H F CF3 F 38 Cl H H F FF 39 Cl H H F CF3 F 40 C4H9 CH2OR Cl F F F 41 C4H9 CH2OR Cl F CF3 F 42CH2CH(NRR′)COOR H H F F F 43 CH2CH(NRR′)COOR H H F CF3 F 44CH2CH(NRR′)COOR F H F F F 45 CH2CN H H F F F 46 CH2CN H H F CF3 F 47CH2CN F H F F F 48 CH2COOH H H F F F 49 CH2COOH H H F CF3 F 50 CH2COOH FH F F F

TABLE 15

Compound No. R^(a2) Rb1 Rb2 Rb3 C1-2-1 H H H H F F F  2 H H H H F CF3 F 3 H H H H F OCF3 F  4 H H H H H H F  5 H H H H CF3 CF3 F  6 H H H H CF3CF3 OCH3  7 H H H H COOR F F  8 H H H H COOR CF3 F  9 H H H H CF2COOR FF 10 H H H H CF2CH2OR F F 11 H H H H CF2CF(CF3)2 F F 12 H H H H FCF(CF3)2 CF3 13 H H H H CF3 F CF(CF3)2 14 H H H H OAlkyl F F 15 H H H HF [OCF2CF(CF3)]nOC3F7 F 16 H H H H F [OCF2CF(CF3)]nOCF2CF═CH2 F 17 H H HH F [OCF2CF(CF3)]nOCF2CFClCF2Cl F 18 H H H H F[OCF2CF(CF3)]nO(CF2)mCFClCF2Cl F 19 H H H H F [OCF2CF(CF3)]nO(CF2)mI F20 H H H H F [OCF2CF(CF3)]nOCF2CF2SO2R F 21 H H H H F[OCF2CF2]nO(CF2)mCFClCF2Cl F 22 H H H H F [OCF2CF2]nO(CF2)mF F 23 H H HH H (CF2)nF F 24 H H H H H (CF2)nI F 25 H H H H F Cl F 26 CH3 H H H F FF 27 CH3 H H H F CF3 F 28 Ph H H H F F F 29 Ph H H H F CF3 F 30 CH3 Ph HH F F F 31 CH3 Ph H H F CF3 F 32 CH2OR H H H F F F 33 CH2OR H H H F CF3F 34 COOR H H H F F F 35 COOR H H H F CF3 F 36 Cl H H H F F F 37 Cl H HH F CF3 F 38 CH(NRR′)COOR H H H F F F 39 CH(NRR′)COOR H H H F CF3 F 40CH(NRR′)COOR F H H F F F 41 CH(NRR′)COOR F H H F CF3 F 42 CH2CH2NRR′ H HH F F F 43 CH2CH2NRR′ H H H F CF3 F 44 CH2CN H H H F F F 45 CH2CN F H HF CF3 F 46 CH2COOH H H H F F F 47 CH2COOH F H H F CF3 F

TABLE 16

Compound No. R^(a3) Rb1 Rb2 Rb3 C-1-3-1 H H H F F F  2 H H H F CF3 F  3H H H F OCF3 F  4 H H H H H F  5 H H H CF3 CF3 F  6 H H H CF3 CF3 OCH3 7 H H H COOR F F  8 H H H COOR CF3 F  9 H H H CF2COOR F F 10 H H HCF2CH2OR F F 11 H H H CF2CF(CF3)2 F F 12 H H H F CF(CF3)2 CF3 13 H H HCF3 F CF(CF3)2 14 H H H OAlkyl F F 15 H H H F [OCF2CF(CF3)]nOC3F7 F 16 HH H F [OCF2CF(CF3)]nOCF2CF═CH2 F 17 H H H F [OCF2CF(CF3)]nOCF2CFClCF2ClF 18 H H H F [OCF2CF(CF3)]nO(CF2)mCFClCF2Cl F 19 H H H F[OCF2CF(CF3)]nO(CF2)mI F 20 H H H F [OCF2CF(CF3)]nOCF2CF2SO2R F 21 H H HF [OCF2CF2]nO(CF2)mCFClCF2Cl F 22 H H H F [OCF2CF2]nO(CF2)mF F 23 H H HH (CF2)nF F 24 H H H H (CF2)nI F 25 H H H F Cl F 26 CH3 H H F F F 27 CH3H H F CF3 F 28 CH3 CH3 H F F F 29 CH3 CH3 H F CF3 F 30 Ph H H F F F 31Ph H H F CF3 F 32 CH3 Ph H F F F 33 CH3 Ph H F CF3 F 34 CH2OR H H F F F35 CH2OR H H F CF3 F 36 COOR H H F F F 37 COOR H H F CF3 F 38 Cl H H F FF 39 Cl H H F CF3 F

TABLE 17

Compound No. R^(a4) Rb1 Rb2 Rb3 C1-4-1 H H F F F  2 H H F CF3 F  3 H H FOCF3 F  4 H H H H F  5 H H CF3 CF3 F  6 H H CF3 CF3 OCH3  7 H H COOR F F 8 H H COOR CF3 F  9 H H CF2COOR F F 10 H H CF2CH2OR F F 11 H HCF2CF(CF3)2 F F 12 H H F CF(CF3)2 CF3 13 H H CF3 F CF(CF3)2 14 H HOAlkyl F F 15 H H F [OCF2CF(CF3)]nOC3F7 F 16 H H F[OCF2CF(CF3)]nOCF2CF═CH2 F 17 H H F [OCF2CF(CF3)]nOCF2CFClCF2Cl F 18 H HF [OCF2CF(CF3)]nO(CF2)mCFClCF2Cl F 19 H H F [OCF2CF(CF3)]nO(CF2)mI F 20H H F [OCF2CF(CF3)]nOCF2CF2SO2R F 21 H H F [OCF2CF2]nO(CF2)mCFClCF2Cl F22 H H F [OCF2CF2]nO(CF2)mF F 23 H H H (CF2)nF F 24 H H H (CF2)nI F 25 HH F Cl F 26 CH3 H F F F 27 CH3 H F CF3 F 28 Ph H F F F 29 Ph H F CF3 F30 COOR H F F F 31 COOR H F CF3 F 32 Cl H F F F 33 Cl H F CF3 F

TABLE 18

Compound No. R^(a6) R^(a5) Rb1 Rb2 Rb3 C1-5-1 H H H H H H F F F  2 H H HH H H F CF3 F  3 H H H H H H H H F  4 H H H H H H CF3 CF3 F  5 H H H H HH CF3 CF3 OCH3  6 F H H H H H F F F  7 F H H H H H F CF3 F  8 COOR H H HH H F F F  9 COOR H H H H H F CF3 F 10 COOR F H H H H F F F 11 COOR F HH H H F CF3 F 12 H H H H COOR H F F F 13 H H H H COOR H F CF3 F 14 F H HH COOR H F F F 15 F H H H COOR H F CF3 F 16 H H H H CH(NRR′)COOR H F F F17 H H H H CH(NRR′)COOR H F CF3 F 18 F H H H CH(NRR′)COOR H F F F 19 F HH H CH(NRR′)COOR H F CF3 F 20 H H H H CH2NRR′ H F F F 21 H H H H CH2NRR′H F CF3 F 22 F H H H CH2NRR′ H F F F 23 F H H H CH2NRR′ H F CF3 F 24 H HH H CN H F F F 25 H H H H CN H F CF3 F 26 F H H H CN H F F F 27 F H H HCN H F CF3 F

TABLE 19

Compound No. R^(a8) R^(a7) Rb1 Rb2 Rb3 C1-6-1 H H H F F F  1 H H H F CF3F  2 H H H H H F  3 H H H CF3 CF3 F  4 H H H CF3 CF3 OCH3  5 COOR H H FF F  6 COOR H H F CF3 F  7 COOR F H F F F  8 COOR F H F CF3 F  9 CH3 H HF F F 10 CH3 H H F CF3 F 11 CH3 F H F F F 12 CH3 F H F CF3 F 13 Ph H H FF F 14 Ph H H F CF3 F 15 Ph F H F F F 16 Ph F H F CF3 F 17 NR2 H H F F F18 NR2 H H F CF3 F 19 OR H H F F F 20 OR H H F CF3 F

TABLE 20

Compound No. Y R^(a9) Rb1 Rb2 Rb3 C1-7-1 ═O ═O H F F F  2 ═O ═O H F CF3F  3 ═O ═O H H H F  4 ═O ═O H CF3 CF3 F  5 ═O ═O H CF3 CF3 OCH3  6 ═O ═OCH3 F F F  7 ═O ═O CH3 F CF3 F  8 ═O ═O Ph F F F  9 ═O ═O Ph F CF3 F 10═O ═O OR F F F 11 ═O ═O OR F CF3 F 12 ═O ═O F F F F 13 ═O ═O F F CF3 F14 ═O NRR′ H F F F 15 ═O NRR′ H F CF3 F 16 ═O NRR′ F F F F 17 ═O NRR′ FF CF3 F 18 ═O OR H F F F 19 ═O OR H F CF3 F 20 ═O F H F F F 21 ═O F H FCF3 F 22 ═O F CH3 F F F 23 ═O F CH3 F CF3 F 24 ═O F2 H F F F 25 ═O F2 HF CF3 F 26 ═O F2 CH3 F F F 27 ═O F2 CH3 F CF3 F 28 ═O F2 Ph F F F 29 ═OF2 Ph F CF3 F 30 ═O F2 OR F F F 31 ═O F2 OR F CF3 F

TABLE 21

Compound No. R^(a11) R^(a10) Rb1 Rb2 Rb3 C1-8-1 H H H H H F F F  2 H H HH H F CF3 F  3 H H H H H H H F  4 H H H H H CF3 CF3 F  5 H H H H H CF3CF3 OCH3  6 COOR H H H H F F F  7 COOR H H H H F CF3 F  8 COOR F H H H FF F  9 COOR F H H H F CF3 F 10 CH3 H H H H F F F 11 CH3 H H H H F CF3 F12 CH3 F H H H F F F 13 CH3 F H H H F CF3 F 14 Ph H H H H F F F 15 Ph HH H H F CF3 F 16 Ph F H H H F F F 17 Ph F H H H F CF3 F 18 H H H H COORF F F 19 H H H H COOR F CF3 F 20 H H H H CN F F F 21 H H H H CN F CF3 F

TABLE 22

Compound No. R^(a10) Rb1 Rb2 Rb3 C1-9-1 H H F F F  2 H H F CF3 F  3 H HF OCF3 F  4 H H H H F  5 H H CF3 CF3 F  6 H H CF3 CF3 OCH3  7 H H COOR FF  8 H H COOR CF3 F  9 H H CF2COOR F F 10 H H CF2CH2OR F F 11 H HCF2CF(CF3)2 F F 12 H H F CF(CF3)2 CF3 13 H H CF3 F CF(CF3)2 14 H HOAlkyl F F 15 H H F [OCF2CF(CF3)]nOC3F7 F 16 H H F[OCF2CF(CF3)]nOCF2CF═CH2 F 17 H H F [OCF2CF(CF3)]nOCF2CFClCF2Cl F 18 H HF [OCF2CF(CF3)]nO(CF2)mCFClCF2Cl F 19 H H F [OCF2CF(CF3)]nO(CF2)ml F 20H H F [OCF2CF(CF3)]nOCF2CF2SO2R F 21 H H F [OCF2CF2]nO(CF2)mCFClCF2Cl F22 H H F [OCF2CF2]nO(CF2)mF F 23 H H H (CF2)nF F 24 H H H (CF2)nI F 25 HH F Cl F 26 CH3 H F F F 27 CH3 H F CF3 F 28 Ph H F F F 29 Ph H F CF3 F30 COOR H F F F 31 COOR H F CF3 F 32 Cl H F F F 33 Cl H F CF3 F

TABLE 23

Compound No. R^(a10) Rb1 Rb2 Rb3 C1-10-1 H F F F  2 H F CF3 F  3 H FOCF3 F  4 H H H F  5 H CF3 CF3 F  6 H CF3 CF3 OCH3  7 H COOR F F  8 HCOOR CF3 F  9 H CF2COOR F F 10 H CF2CH2OR F F 11 H CF2CF(CF3)2 F F 12 HF CF(CF3)2 CF3 13 H CF3 F CF(CF3)2 14 H OAlkyl F F 15 H F[OCF2CF(CF3)]nOC3F7 F 16 H F [OCF2CF(CF3)]nOCF2CF═CH2 F 17 H F[OCF2CF(CF3)]nOCF2CFClCF2Cl F 18 H F [OCF2CF(CF3)]nO(CF2)mCFClCF2Cl F 19H F [OCF2CF(CF3)]nO(CF2)mI F 20 H F [OCF2CF(CF3)]nOCF2CF2SO2R F 21 H F[OCF2CF2]nO(CF2)mCFClCF2Cl F 22 H F [OCF2CF2]nO(CF2)mF F 23 H H (CF2)nFF 24 H H (CF2)nI F 25 H F Cl F 26 F F F F 27 F F CF3 F 28 CH3 F F F 29CH3 F CF3 F 30 Ph F F F 31 Ph F CF3 F 32 COOR F F F 33 COOR F CF3 F

TABLE 24

Compound No. R^(a11) R^(a10) Rb1 Rb2 Rb3 C1-11-1 H H H H H H F F F  2 HH H H H H F CF3 F  3 H H H H H H H H F  4 H H H H H H CF3 CF3 F  5 H H HH H H CF3 CF3 OCH3  6 F H H H H H F F F  7 F H H H H H F CF3 F  8 COOR HH H H H F F F  9 COOR H H H H H F CF3 F 10 COOR F H H H H F F F 11 COORF H H H H F CF3 F 12 H H H H COOR H F F F 13 H H H H COOR H F CF3 F 14 FH H H COOR H F F F 15 F H H H COOR H F CF3 F 16 H H H H CH(NRR′)COOR H FF F 17 H H H H CH(NRR′)COOR H F CF3 F 18 F H H H CH(NRR′)COOR H F F F 19F H H H CH(NRR′)COOR H F CF3 F 20 H H H H CH2NRR′ H F F F 21 H H H HCH2NRR′ H F CF3 F 22 F H H H CH2NRR′ H F F F 23 F H H H CH2NRR′ H F CF3F 24 H H H H CN H F F F 25 H H H H CN H F CF3 F 26 F H H H CN H F F F 27F H H H CN H F CF3 F

TABLE 25

Compound No. R^(a11) R^(a10) Rb1 Rb2 Rb3 C1-12-1 H H H H H F F F  2 H HH H H F CF3 F  3 H H H H H H H F  4 H H H H H CF3 CF3 F  5 H H H H H CF3CF3 OCH3  6 F H H H H F F F  7 F H H H H F CF3 F  8 F H H H CH3 F F F  9F H H H CH3 F CF3 F 10 H H H H CH3 F F F 11 F H H H CH3 F CF3 F 12 COORH H H H F F F 13 COOR H H H H F CF3 F 14 CH3 H H H H F F F 15 CH3 H H HH F CF3 F 16 Ph H H H H F F F 17 Ph H H H H F CF3 F 18 H H H H COOR F FF 19 H H H H COOR F CF3 F 20 F H H H COOR F F F 21 F H H H COOR F CF3 F22 H H H H CN F F F 23 H H H H CN F CF3 F 24 F H H H CN F F F 25 F H H HCN F CF3 F

TABLE 26

Compound No. R^(a11) Rb1 Rb2 Rb3 C1-13-1 H H H H F F F  2 H H H H F CF3F  3 H H H H H H F  4 H H H H CF3 CF3 F  5 H H H H CF3 CF3 OCH3  6 F H HH F F F  7 F H H H F CF3 F  8 F F H H F F F  9 F F H H F CF3 F 10 COOR HH H F F F 11 COOR H H H F CF3 F 12 CH3 H H H F F F 13 CH3 H H H F CF3 F14 Ph H H H F F F 15 Ph H H H F CF3 F 16 OR H H H F F F 17 OR H H H FCF3 F

Among these compounds, the following novel compounds which are notdisclosed in prior art documents are especially preferable from theviewpoint of easy synthesis and availability.

Fluorine-containing imidazole compounds represented by the structuralformula (C-1):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf^(c1) is thesame as the formula (c) or is a monovalent organic group which may haveat least one residue defined by deleting Rf^(c1) group from the formula(C-1); Rf^(c1) is not —CFHCF₃, —CF₂CFZ¹H and —CF═CFZ¹ (Z¹ is F or Cl).

R^(a)s are the same or different, and each is preferably H, F, Cl, —CH₃,—C₂H₅, —C₃H₇, —C₄H₉, —COOR, —CN, -Ph (phenyl group), —CH₂CN, —CH₂COOR,—CH₂SR, —CH₂CH(NR₂)COOR, —(CF)_(n)F, —(CF)_(n)H, —CF₂CF(CF₃)H or—(CF₂CH₂)_(n)H (Rs are the same or different, and each is a hydrocarbongroup having 1 to 10 carbon atoms; n is an integer of 1 to 10,000).

Preferable example of Rf^(c1) is one represented by the formula (c-1):

wherein R^(c-1a) and R^(c-1b) are the same or different, and each is F,—(CF₂)_(q)F, —O(CF₂)_(q)F, —CF(CF₃)₂, —(OCF₂CF(CF₃))_(p)—O(CF₂)_(q)F,—(OCF₂CF(CF₃))_(p)—OCF₂CF₂CF═CH₂, —(OCF₂CF(CF₃))_(p)—OCF₂CF₂CF₂CH₂I,—(OCF₂CF(CF₃))_(p)—O(CF₂)_(q)CFClCF₂Cl,—(OCF₂CF(CF₃))_(p)—O(CF₂)_(q)CF₂I,—(CF₂)_(q)—(OCF(CF₃)CF₂)_(p)OCF(CF₃)COOR,—(CF₂)_(q)—(OCF(CF₃)CF₂)_(p)OCF(CF₃)CH₂OR,—(CF₂CF₂)_(l)—(CF₂CF(CF₃))_(m)—(CF₂CH₂)_(n)-A,—(OCF₂CF(CF₃))_(x)—(OCF₂CF₂)_(y)—(OCF₂CF₂CF₂)_(z)—(OCF₂CF₂CH₂)_(w)-A,—CF₂CHFOCF₂CF₂CF═CF₂—B or —CF₂CH₂—(CF₂)_(r)—CH₂CF₂—B (Rs are the same ordifferent, and each is a monovalent hydrocarbon group having 1 to 10carbon atoms; A is H, F or a polymer end group; B is a residue definedby deleting Rf^(c1) group from the formula (C-1); q is independently aninteger of 1 to 9 in each formula; p is independently 0 or an integer of1 to 20 in each formula; r is an integer of 1 to 10,000; each of l, mand n is independently 0 or an integer of 1 to 5,000, and the sum of l,m and n is an integer of 10 to 10,000; each of w, x, y and z isindependently 0 or an integer of 1 to 30, and the sum of w, x, y and zis an integer of 3 to 60; R^(c-1c) is F, H, —CF₃, —CF(CF₃)₂ or—CF₂CF(CF₃)₂; R^(c-1a), R^(c-1b) and R^(c-1c) are not F at the sametime.Fluorine-containing pyrrole compounds represented by the structuralformula (C-2):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf^(c2) is thesame as the formula (c) or is a monovalent organic group which may haveat least one residue defined by deleting Rf^(c2) group from the formula(C-2); Rf^(c2) is not —CFHCF₃, —CF₂CZ¹Z²H and —CF═CFZ¹ (Z¹ is F or Cl;Z² is H, F, Cl, an alkyl group, a fluorinated alkyl group or achlorinated alkyl group).

Preferable examples of R^(a) and Rf^(c2) are the same as R^(a) andRf^(c1), respectively of the structural formula (C-1).

Fluorine-containing pyrazole compounds represented by the structuralformula (C-3):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf^(c3) is thesame as the formula (c) or is a monovalent organic group which may haveat least one residue defined by deleting Rf^(c3) group from the formula(C-3); Rf^(c3) is not —CFHCF₃, —CF₂CFZ¹H and —CF═CFZ¹ (Z¹ is F or Cl).

Preferable examples of R^(a) and Rf^(c3) are the same as R^(a) andRf^(c1), respectively of the structural formula (C-1).

Fluorine-containing triazole compounds represented by the structuralformula (C-4):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf^(c4) is thesame as the formula (c) or is a monovalent organic group which may haveat least one residue defined by deleting Rf^(c4) group from the formula(C-4); Rf^(c4) is not —CFHCF₃, —CF₂CFZ¹H and —CF═CFZ¹ (Z¹ is F or Cl).

Preferable examples of R^(a) and Rf^(c4) are the same as R^(a) andRf^(c1), respectively of the structural formula (C-1).

Fluorine-containing indole compounds represented by the structuralformula (C-5):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring and/or the aromatic ring aresubstituted by them; Rf^(c5) is the same as the formula (c) or is amonovalent organic group which may have at least one residue defined bydeleting Rf^(c5) group from the formula (C-5); Rf^(c5) is not —CFHCF₃,—CF₂CZ¹Z²H and —CF═CFZ¹ (Z¹ is F or Cl; Z² is H, F, Cl, an alkyl group,a fluorinated alkyl group or a chlorinated alkyl group).

Preferable examples of R^(a) and Rf^(c5) are the same as R^(a) andRf^(c1), respectively of the structural formula (C-1).

Fluorine-containing purine compounds represented by the structuralformula (C-6):

wherein each of R^(a) is halogen atom, a functional group or an organicgroup and may be present or may not be present, and when R^(a)s arepresent, the whole or a part of hydrogen atoms of the heteroaromaticring and/or the aromatic ring are substituted by them; Rf^(c6) is thesame as the formula (c) or is a monovalent organic group which may haveat least one residue defined by deleting Rf^(c6) group from the formula(C-6); Rf^(c6) is not —CFHCF₃, —CF₂CFZ¹H and —CF═CFZ¹ (Z¹ is F or Cl).

Preferable examples of R^(a) and Rf^(c6) are the same as R^(a) andRf^(c1), respectively of the structural formula (C-1).

Fluorine-containing purine derivatives represented by the structuralformula (C-7):

wherein R^(a) is halogen atom, a functional group or an organic groupand may be present or may not be present; Ys are the same or differentand each is ═O, —NRR′, —OR, F or F₂; R and R′ are the same or differentand each is hydrogen atom, an alkyl group, an arylalkyl group, anorganosilicon group, an alkoxyl group or a carboxyester group; Rf^(c7)is the same as the formula (c) or is a monovalent organic group whichmay have at least one residue defined by deleting Rf^(c7) group from theformula (C-7); Rf^(c7) is not —CFHCF₃, —CF₂CFZ¹H and —CF═CFZ¹ (Z¹ is For Cl).

Preferable examples of R^(a) and Rf^(c7) are the same as R^(a) andRf^(c1), respectively of the structural formula (C-1).

In those heteroaromatic ring compounds (C1) which are novel compounds,preferable examples of Rf^(c1) to Rf^(c7) in the fluoroalkyl grouprepresented by the formula (c) are those having at least one kind of theunits represented by the formulas (b-1) to (b-5) as Rb¹ to Rb³ of thefluoroalkene (B) and/or those having the polymerizable group (b-6) atthe end of at least one of R^(b1) to R^(b3). Preferable example of thepolymerizable group is a carbon-carbon double bond.

Among the above-mentioned heteroaromatic ring compounds (C1) which arenovel compounds, those having CF₃ group or oxygen atom as the Rf groupare preferable as a starting material functioning to lower crystallinityand provide an ionic liquid having a low melting point. Especiallypreferable are Rf groups having two or more CF₃ groups or two or moreoxygen atoms.

The second preparation process of the present invention is the processfor preparing the salt (E) having an heteroaromatic ring structurehaving a N—Rf group in its ring, which is characterized in that a saltforming compound (D) is acted on the heteroaromatic ring compound (C)having a N—Rf group in its ring and obtained by the above-mentionedfirst preparation process, and if necessary, anion exchanging is carriedout.

Examples of the salt forming compound (D) are, for instance, acids oralkylating agents represented by the formula (D1): Rd—X¹.

In the case of acids (Rd═H), inorganic acids such as HF, HCl, HBr, HI,HClO₄, HNO₃, H₂CO₃, H₂SO₄, HBF₄, HPF₆, HSbF₆, HAlCl₄, HAlF₄, HAsF₆ andHSO₃F, and organic acids such as R—SO₃H, R—COOH and R—PO₃H can be used.

In addition, in the case of alkylating agents (Rd is an alkyl group),there are compounds having X¹ of F, Cl, Br, I, —OSO₂R, —OCO₂R, —OCOR or—OPO₃R (R is a monovalent hydrocarbon group).

Examples of Rd are, for instance, hydrogen atom; linear or branchedalkyl groups having 1 to 10 carbon atoms such as CH₃, C₂H₅, n-C₃H₇,i-C₃H₇ and C₄H₉; linear or branched fluoroalkyl groups having a unitsuch as CF₃, C₂F₅, n-C₃F₇, i-C₃F₇, C₄F₉, CF₂CF₂Cl, CF₂CF₂Br, CF₂CF₂I,CH₂CF₃, (CF₂CF₂)_(v)H (v is an integer of 1 to 5), CF₂CHFCF₃, CF₂CH₃,CF₂CFClH, CF₂CH(CF₃)₂, CF₃CH₂CH₂, C₂F₅CH₂CH₂, n-C₃F₇CH₂CH₂,i-C₃F₇CH₂CH₂, C₄F₉CH₂CH₂, C₄F₉CH₂CH₂, —CH₂CH₂C₂F₄CH₂CH₂—,—CH₂CH₂C₄F₈CH₂CH₂— or —CH₂CH₂C₆F₁₂CH₂CH₂—; linear or branchedhydroxyalkyl groups which may have fluorine and has a unit such as—(CF₂)_(v)CH₂—OR (v is 0 or an integer of 1 to 10; R is hydrogen atom oran alkyl group which may be substituted by hydrogen atom or halogenatom), —CH₂(CF₂CF₂)_(v)CH₂—OR (v is an integer of 1 to 5; R is hydrogenatom or an alkyl group which may be substituted by hydrogen atom orhalogen atom), —CH₂CH₂(CF₂CF₂)_(v)CH₂—OR (v is an integer of 1 to 5; Ris hydrogen atom or an alkyl group which may be substituted by hydrogenatom or halogen atom), —CH₂CH₂(CF₂CF₂)_(v)CH₂CH₂—OR (v is an integer of1 to 5; R is hydrogen atom or an alkyl group which may be substituted byhydrogen atom or halogen atom) or —CH₂(CF₂CF₂)_(v)CH₂CH₂—OR (v is aninteger of 1 to 5; R is hydrogen atom or an alkyl group which may besubstituted by hydrogen atom or halogen atom).

With respect to the reaction conditions for allowing the salt formingcompound (D) to act on the heteroaromatic ring compound, there can beemployed usual conditions for salt forming reaction or alkylationreaction which are described in, for example, Y. L. Yagupolskii et al.,J. Fluorine Chem., 126, pp. 669-672 (2005), C. E. Song et al., Chem.Comm., p. 1695 (2000), R. Hagiwara et al., J. Fluorine Chem., 99, p. 1(1999), A. E. Visser et al., Green Chem., 2, p. 1 (2000) and M.Yoshizawa et al., Electrochem. Solid-State Lett., 4, E25 (2001).

For example, in the case where an acid is used as the salt formingcompound (D), it is preferable to carry out the reaction at a reactiontemperature of −30° C. to 150° C. in the absence of a solvent or byusing a solvent such as diethyl ether, t-butyl methyl ether, diisopropylether, dibutyl ether, tetrahydrofuran, dioxane, dimethoxyethane,diglyme, triglyme, tetraglyme, ethyl acetate, methyl acetate, propylacetate, butyl acetate, dimethyl sulfoxide, sulfolane, benzene, toluene,xylene, chloroform, methylene chloride, dichloroethane, trichloroethane,dichloropentafluoropropane, dichlorofluoroethane,trichlorotrifluoroethane, tetrachlorohexafluorobutane,dichlorooctafluorobutane, pentachloropentafluorohexane,dibromotetrafluoroethane, perfluorohexane, perfluoro(butyltetrahydrofuran) or perfluorotributylamine, though it depends on kind ofthe fluorine-containing heteroaromatic ring compound (C) (salt formingmethod 1).

In addition, in the case where an alkylating agent is used as the saltforming compound (D), it is preferable to carry out the reaction at areaction temperature of −30° C. to 150° C. in the absence of a solventor by using a solvent such as diethyl ether, t-butyl methyl ether,diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane,dimethoxymethane, dimethoxyethane, diglyme, triglyme, tetraglyme,N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, ethylacetate, methyl acetate, propyl acetate, butyl acetate, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, benzene, toluene,xylene, chloroform, methylene chloride, dichloroethane, trichloroethane,dichloropentafluoropropane, dichlorofluoroethane,trichlorotrifluoroethane, tetrachlorohexafluorobutane,dichlorooctafluorobutane, pentachloropentafluorohexane,dibromotetrafluoroethane, perfluorohexane, perfluoro(butyltetrahydrofuran) or perfluorotributylamine, though it depends on kind ofthe fluorine-containing heteroaromatic ring compound (C) (salt formingmethod 2).

When the fluorine-containing heteroaromatic ring compound (C) is acompound having an imidazole skeleton, for example, thefluorine-containing imidazole compound (C1-1) or the fluorine-containingbenzimidazole compound, the fluorine-containing purine compound (C-6) orthe fluorine-containing purine derivative (C-7), the above-mentionedsalt forming reaction proceeds especially satisfactorily, and Rd isbonded to nitrogen atom other than N—Rf of the fluorine-containingheteroaromatic ring to give a cation and X¹ becomes a counter anion.

Further, the counter anion can be changed to various anions, ifnecessary, by anion exchange of the counter anion of the salt offluorine-containing heteroaromatic ring compound obtained by allowingsuch a salt forming compound (D) to act on the heteroaromatic ringcompound.

Examples of a compound usable for the anion exchange are, for instance,M-ClO₄, M-NO₃, M₂-SO₄, M₂-CO₃, M-BF₄, M-BCl₄, M-PF₆, M-SbF₆, M-AlCl₄,M-Al₂Cl₇, M-AlF₄, M-AsF₆, M-N(CN)₂, M-F, a mixture of M-F and HF,M-N(SO₂R)(SO₂R′), M-OSO₂R, M-OCOR, M-OPO₃R, M-C(SO₂R)₂(SO₂R′) andM-[RCOCHCOR′], wherein R and R′ are the same or different and each is—(CF₂)_(n)F (n=1 to 20), —CF(CF₃)OCF₃,—CF(CF₃)—[OCF₂CF(CF₃)]_(n)—O(CF₂)_(m)—F,—CF(CF₃)—[OCF₂CF(CF₃)]_(n)—O(CF₂)—CFClCF₂Cl,—CF(CF₃)—[OCF₂CF(CF₃)]_(n)—O(CF₂)_(m)—CF₂I,—CF(CF₃)—[OCF₂CF(CF₃)]_(n)—OCF₂CF₂CF═CH₂,—CF(CF₃)—[OCF₂CF(CF₃)]_(n)—OCF₂CF₂CF₂CH₂I,—CF(CF₃)—[OCF₂CF(CF₃)]_(n)—OCF₂CF₂SO₂X,—(CF₂)_(m)—[OCF(CF₃)CF₂]_(n)OCF(CF₃)COOX,—(CF₂)_(m)—[OCF(CF₃)CF₂]_(n)OCF(CF₃)CH₂OX,—(CF₂CF₂)_(p)—(CF₂CF(CF₃))_(q)—(CF₂CH₂)_(r)—(CF₂CFCl)_(s)-A, or—(OCF₂CF(CF₃))_(x)—(OCF₂CF₂)_(y)—(OCF₂CF₂CF₂)_(z)—(OCF₂CF₂CH₂)_(w)—(OCF₂)_(v)-A(in these formulas, A represents H, F, an end group of a polymerizationinitiator or a modified group thereof; n and m are the same or differentand each is 0 or an integer of 1 to 10; each of p, q, r and s isindependently 0 or an integer of 1 to 5,000, and the sum of p, q, r ands is an integer of 10 to 10,000; each of x, y, z, v and w isindependently 0 or an integer of 1 to 60, and the sum of x, y, z, w andv is an integer of 3 to 60); M is Li, Na, K, Rb, Cs, ½Mg, ⅓Al, Ag, ½Zn,½Ni, ⅓Fe, H or NH₄.

In addition, the compound may be a polymer chain containing 1 to 100% bymass of a polymer unit represented by:

wherein X is H or F; R is H, F, CH₃ or CF₃; Q is -Q¹⁻,—[OCF₂CF(CF₃)]₀₋₁₀O(CF₂)₀₋₈-Q¹⁻, —(CF₂)₀₋₈[OCF(CF₃)CF₂]₀₋₁₀OCF(CF₃)-Q¹⁻,(CH₃)₀₋₈(CF₂)₀₋₂₀(CH₃)₀₋₈-Q¹⁻ or —(C₆H₄)(CH₃)₀₋₈-Q¹⁻ (Q¹⁻s are the sameor different and each is COO⁻ or SO³⁻). It is desirable that a numberaverage molecular weight of the polymer chain is about 1×10³ to about8×10⁵, from the viewpoint of solubility of the polymer in a solvent.

A copolymerizable comonomer is not limited particularly, and may beoptionally selected depending on characteristics intended to beimparted. Nonlimiting examples of preferable comonomers are, forinstance, CF₂═CF₂, CF₂═CF(CF₃), CF₂═CFCl, CF₂═CH₂, CF₂═CFH,perfluoro(butenyl vinyl ether), perfluoro-2,2-dimethyldioxole,perfluorodioxole, CH₂═CH₂, CH₂═CH(CH₃), CH₂═CHCH═CH₂, CH₂═CHCl,CH₂═CCl₂, CH₂═CHCO₂R (R is hydrogen atom or an alkyl group which may besubstituted by hydrogen atom or halogen atom), CH₂═C(CH₃)CO₂R (R ishydrogen atom or an alkyl group which may be substituted by hydrogenatom or halogen atom), CH₂═CFCO₂R (R is hydrogen atom or an alkyl groupwhich may be substituted by hydrogen atom or halogen atom),CH₂═C(CF₃)CO₂R (R is hydrogen atom or an alkyl group which may besubstituted by hydrogen atom or halogen atom), CH₂═CHC₆X₅ (X is H or F),CH₂═C(CH₃)C₆X₅ (X is H or F), CH₂═CFC₆X₅ (X is H or F), CH₂═C(CF₃)C₆X₅(X is H or F), CH₂═CHCN, CH₂═C(CH₃)CN, CH₂═CFCN, CH₂═C(CF₃)CN,CH₂═CHOCO₂R (R is an alkyl group which may be substituted by hydrogenatom or halogen atom), CH₂═CHOR (R is an alkyl group which may besubstituted by hydrogen atom or halogen atom),CH₂═CFCF₂CF₂CF₂O[CF(CF₃)CF₂]_(n)OCF(CF₃)COOR (n is 0 or an integer of 1to 20; R is hydrogen atom or an alkyl group which may be substituted byhydrogen atom or halogen atom),CH₂═CFCF₂CF₂O[CF(CF₃)CF₂]_(n)OCF(CF₃)CH₂OR (n is 0 or an integer of 1 to20; R is hydrogen atom or an alkyl group which may be substituted byhydrogen atom or halogen atom), CH₂═CFCF₂CF₂O[CF(CF₃)CF₂]_(n)OCFCF₃ (nis 0 or an integer of 1 to 20), sulfur dioxide, ethylene oxide,propylene oxide, tetrafluoroethylene oxide, hexafluoropropylene oxide,fluorophosgene and hexafluoroacetone.

Examples of the salt (E) of fluorine-containing heteroaromatic ringcompound so-obtained by acting the salt forming compound (D) and ifnecessary, conducting anion exchange are, for instance, a salt ofheteroaromatic ring compound represented by the formula (E1):

wherein

is a moiety forming a heteroaromatic ring together with a nitrogen atomand the whole or a part of its hydrogen atoms may be substituted by thesame or different organic groups; Rf is Rf^(e) where Rf^(e) is the sameas the formula (c) or is a monovalent organic group which may have atleast one residue defined by deleting Rf group from the formula (E1); Rdis H or a monovalent organic group; X is a counter anion.

Examples of the salt (E) represented by the formula (E1) are fluoride,chloride, bromide, iodide, perchlorate, nitrate, sulfate, carbonate,tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate,tetrachloroaluminate, tetrafluoroaluminate, hexafluoroarsenate,fluorosulfonate, dicyanamide salt, F(HF)_(n) salt (n=1 to 10),bisperfluoro(C1 to C20)alkylsulfonylamide salt (two alkyl groups are thesame or different), perfluoro(C1 to C20)alkylsulfonate, perfluoro(C1 toC20)alkylcarboxylate, perfluoro(C1 to C20)alkylphosphonate,trisperfluoro(C1 to C20)alkylsulfonyl carbonate (three alkyl groups arethe same or different), 1-perfluoroalkyl-3-perfluoro(C1 to C10)alkyl-1,3-diketonate (two alkyl groups are the same or different),dichlorocuprate, tetrachloroborate, heptachlorodialuminate andtrichlorozincate of the fluorine-containing heteroaromatic ring compound(C).

Especially the salt of fluorine-containing imidazole compoundrepresented by the structural formula (E-1):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; Rf^(c1) is thesame as the formula (c) or is a monovalent organic group which may haveat least one residue defined by deleting Rf^(c1) group from the formula(C-1); Rf^(c1) is not —CF₂CF₂H, —CF═CF₂, —CF₂CFClH, —CF₂═CFCl and—CFHCF₃; Rd is H or a monovalent organic group; X is a counter anion, isa novel compound.

In the formula (E-1), preferable examples of R^(a), Rf^(c1), Rd and Xare those raised supra. Rf^(c1) is preferably one having theperfluoroalkylene group of the formula (b-4) having a branched chainand/or the fluoroether unit of the formula (b-5), especially preferablyone which has the perfluoroalkylene group of the formula (b-4) having abranched chain and two or more CF₃ groups or two or more oxygen atomsand/or the fluoroether unit of the formula (b-5) since a liquid state iseasily exhibited at room temperature.

In addition, the end of at least one of R^(a) and Rf^(c1) may be thepolymerizable group (b-6). Examples of the polymerizable group are, forinstance, a carbon-carbon double bond, a hydroxyl group, a carboxylgroup, an amino group, an isocyanate group, a thiol group and athioisocyanate group, and especially preferable is a carbon-carbondouble bond.

The heteroaromatic ring compound (C) having a N—Rf group in its ringwhich is prepared by the first preparation process of the presentinvention not only is useful as a starting material for the secondpreparation process but also can be expected as various materialscomprising a heteroaromatic ring compound having a stable N—Rf group inthe ring thereof, for example, curing agents such as an epoxy resin anda polyurethane resin, various agricultural chemicals, intermediates formedicines such as antibiotics and anti-AIDS drugs and intermediates ofdyes.

The salt (E) of heteroaromatic ring compound having a N—Rf group in itsring which is prepared by the second preparation process of the presentinvention can be used as various materials comprising a heteroaromaticring compound having a stable N—Rf group in the rings thereof, forexample, ionic liquids having various functions useful for electrolytesfor fuel cell, secondary battery, capacitor, dye-sensitized solar celland electrochromic device, and reaction media, catalysis, and chemicalseparation and reprocessing of nuclear fuel, and in addition, can beexpected to be curing agents such as an epoxy resin and a polyurethaneresin, various agricultural chemicals, intermediates for medicines suchas antibiotics and anti-AIDS drugs and intermediates of dyes.

It is known that usually when a hydrocarbon ionic liquid is mixed to aperfluoro solvent, it is separated and are not mixed to each other, andan ionic liquid having a fluoroalkyl chain has an effect of dispersing ahydrocarbon ionic liquid in a perfluoro solvent (T. L. Merrigan et al.,Chem. Comm., pp. 2051-2052 (2000)), and it is also known that when ahydrocarbon ionic liquid is mixed to Nafion (trade mark of Du Pont)which is a fluorine-containing resin having a sulfonic acid group,cation exchange occurs and there is an effect that properties as anelectrolyte rather than properties as a solvent are exhibited (T.Schafer, et al., Chem. Comm., pp. 2594-2096 (2005). In suchapplications, it can be considered that when an ionic liquid having afluoroalkyl chain is used for resins having a high content of fluorineatoms, cation exchange can be carried out more effectively.

Therefore, even if the salt (E) of heteroaromatic ring compound having aN—Rf group in its ring is a solid at normal temperature, as described inthe above-mentioned publications, by dispersing or dissolving the salt(E) of heteroaromatic ring compound having a N—Rf group in its ring in apolymer, a solvent or an ionic liquid, ionic conductivity and a functionof accelerating dispersion of additives can be exhibited byparticipation of a structure of N—Rf group.

EXAMPLES

The present invention is then explained by means of examples, but is notlimited thereto.

Measuring methods used in the present invention are as follows.

(Method of Identification of Compound)

Compounds are identified by ¹H-NMR analysis, ¹⁹F-NMR analysis, IRanalysis and elementary analysis.

NMR measuring equipment: available from BRUKER¹H-NMR measuring condition: 300 MHz (tetramethylsilane ═0 ppm)¹⁹F-NMR measuring condition: 282 MHz (trichlorofluoromethane=0 ppm)IR analysis: Measurement is carried out at room temperature with aFourier-transform infrared spectrophotometer 1760X available from PerkinElmer Co., Ltd.

Example 1

Into a 50 ml autoclave was poured 6.81 g of imidazole (100 mmol, meltingpoint: 89° C.), and evacuation and replacement of atmosphere in theautoclave with nitrogen gas were carried out three times. After theinside of a system was evacuated, tetrafluoroethylene (TFE) wasintroduced until the inside pressure of the system reached 0.1 MPa·G.Then the temperature of the reaction system was increased to 100° C.which was higher than the melting point of imidazole, and TFE wasfurther introduced to maintain the inside pressure of the reactionsystem at 0.3 to 0.5 MPa·G. Supply of TFE was stopped when the amount ofTFE reached 1.1 equivalents (11 g=110 mmol) to imidazole, and stirringwas continued at 100° C. Eight hours after starting of the stirring, theinside of the reaction system was brought to room temperature, followedby evacuation and then distillation in such a state to obtain 14.5 g ofdistillate at 93° C./96 mmHg (yield: 86%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,2-tetrafluoroethyl)imidazole. To this crude reaction productwas added ethyl trifluoroacetate (2.84 g=20 mmol), and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 98%.

¹⁹F-NMR (CD₃COCD₃): δ−102.3 (2F), −142.3 (2F) ppm

¹H-NMR (CD₃COCD₃): δ6.82 (1H, tt), 7.18 (1H, s), 7.48 (1H, s), 8.04 (1H,s) ppm

Example 2

Into a 50 ml autoclave were poured 1.36 g (20 mmol) of imidazole andtetrahydrofuran (30 ml), and the inside of the autoclave was cooled to−78° C., and evacuation and replacement of atmosphere in the autoclavewith nitrogen gas were carried out three times. After the inside of asystem was evacuated, TFE was introduced until the inside pressure ofthe system reached 0.1 MPa·G. Then the temperature of the reactionsystem was increased to 100° C. which was higher than the melting pointof imidazole, and TFE was further introduced to maintain the insidepressure of the reaction system at 0.3 to 0.5 MPa·G. Supply of TFE wasstopped when the amount of TFE reached 1.1 equivalents (2.2 g=22 mmol)to imidazole, and stirring was continued at 100° C. Fifteen hours afterstarting of the stirring, the inside of the reaction system was broughtto room temperature, followed by evacuation, and ethyl trifluoroacetate(1.42 g=10 mmol) was added to this crude reaction product. Yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 89%.

Example 3

Into a 50 ml autoclave were poured 6.81 g (100 mmol) of imidazole andtetrahydrofuran (1.0 ml) as a melting point depressor, and the inside ofthe autoclave was cooled to −78° C., and evacuation and replacement ofatmosphere in the autoclave with nitrogen gas were carried out threetimes. After the inside of a system was evacuated, TFE was introduceduntil the inside pressure of the system reached 0.1 MPa·G. Then thetemperature of the reaction system was increased to 50° C., and TFE wasfurther introduced to maintain the inside pressure of the reactionsystem at 0.3 to 0.5 MPa·G. Supply of TFE was stopped when the amount ofTFE reached 1.1 equivalents (11 g=110 mmol) to imidazole, and stirringwas continued at 50° C. Eight hours after starting of the stirring, theinside of the reaction system was brought to room temperature, followedby evacuation to terminate the reaction. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 92%.

Comparative Example 1

Into a 50 ml autoclave were poured 10.6 g (100 mmol) of potassium saltof imidazole and tetrahydrofuran (30 ml), and the inside of theautoclave was cooled to −78° C., and evacuation and replacement ofatmosphere in the autoclave with nitrogen gas were carried out threetimes. After the inside of a system was evacuated, TFE was introduceduntil the inside pressure of the system reached 0.1 MPa·G. Then thetemperature of the reaction system was increased to 100° C., and TFE wasfurther introduced to maintain the inside pressure of the reactionsystem at 0.3 to 0.5 MPa·G. Supply of TFE was stopped when the amount ofTFE reached 1.1 equivalents (11 g=110 mmol) to the potassium salt ofimidazole, and stirring was continued at 100° C. Fifteen hours afterstarting of the stirring, the inside of the reaction system was broughtto room temperature, followed by evacuation to terminate the reaction.To this crude reaction product was added 2.84 g (20 mmol) of ethyltrifluoroacetate, and it was confirmed by a ¹⁹F-NMR analysis based onethyl trifluoroacetate that 1-(1,1,2,2-tetrafluoroethyl)imidazole hadbeen produced at yield of 13% and 1-(1,2,2-trifluoroethenyl)imidazolehad been produced at yield of 56%. Also according to gas chromatographyanalysis, it was confirmed that the remaining imidazole was 14%.

Then the entire crude reaction product was poured into water (30 ml),and subjected to extraction with ethyl acetate. After separation of anorganic layer, drying was carried out with magnesium sulfate andconcentration was conducted under reduced pressure. Then thereto wasadded 1.46 g (10 mmol) of benzotrifluoride, and it was confirmed by a¹⁹F-NMR analysis based on benzotrifluoride that1-(1,1,2,2-tetrafluoroethyl)imidazole had been produced at yield of 7%and 1-(1,2,2-trifluoroethenyl)imidazole had been produced at yield of39%.

Comparative Example 2

Into a 50 ml autoclave were poured 0.20 g (5 mmol) of metallic potassiumand tetrahydrofuran (10 ml), and the inside of the autoclave was cooledto −78° C., and evacuation and replacement of atmosphere in theautoclave with nitrogen gas were carried out three times. Then theretowas added a solution obtained by dissolving 1.36 g (20 mmol) ofimidazole in tetrahydrofuran (10 ml) at 10° C. over 30 minutes underpressurized nitrogen atmosphere. Thereafter tetrafluoroethylene (TFE)was introduced until the inside pressure of the system reached 0.1MPa·G. Then the temperature of the reaction system was increased to 100°C., and TFE was further introduced to maintain the inside pressure ofthe reaction system at 0.3 to 0.5 MPa·G. Supply of TFE was stopped whenthe amount of TFE reached 1.1 equivalents (2.2 g=22 mmol) to imidazole,and stirring was continued at 100° C. Eight hours after starting of thestirring, the inside of the reaction system was brought to roomtemperature, followed by evacuation to terminate the reaction. To thiscrude reaction product was added 1.42 g (10 mmol) of ethyltrifluoroacetate, and it was confirmed by a ¹⁹F-NMR analysis based onethyl trifluoroacetate that 1-(1,1,2,2-tetrafluoroethyl)imidazole hadbeen produced at yield of 55% and 1-(1,2,2-trifluoroethenyl)imidazolehad been produced at yield of 23%. Also according to gas chromatography,it was confirmed that the remaining imidazole was 9%.

Then the entire crude reaction product was poured into water (30 ml),and subjected to extraction with ethyl acetate. After separation of anorganic layer, drying was carried out with magnesium sulfate andconcentration was conducted under reduced pressure. Then thereto wasadded 1.46 g (10 mmol) of benzotrifluoride, and it was confirmed by a¹⁹F-NMR analysis based on benzotrifluoride that1-(1,1,2,2-tetrafluoroethyl)imidazole had been produced at yield of 41%and 1-(1,2,2-trifluoroethenyl)imidazole had been produced at yield of19%.

Example 4

Into a 50 ml autoclave was poured 6.81 g (100 mmol) of imidazole, andevacuation and replacement of atmosphere in the autoclave with nitrogengas were carried out three times at room temperature. After the insideof a system was evacuated, hexafluoropropylene (HFP) was introduceduntil the inside pressure of the system reached 0.1 MPa·G. Then thetemperature of the reaction system was increased to 100° C. which washigher than the melting point of imidazole, and HFP was furtherintroduced to maintain the inside pressure of the reaction system at 0.3to 0.5 MPa·G. Supply of HFP was stopped when the amount of HFP reached1.1 equivalents (17 g=110 mmol) to imidazole, and stirring was continuedat 100° C. Eight hours after starting of the stirring, the inside of thereaction system was brought to room temperature, followed by evacuationand then distillation in such a state to obtain 16.5 g of distillate at93° C./53 mmHg (yield: 76%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,3,3,3-hexafluoropropyl)imidazole. To this crude reactionproduct was added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yieldby a ¹⁹F-NMR analysis based on ethyl trifluoroacetate was 83%.

¹⁹F-NMR (CD₃COCD₃): δ−73.9 (3F), −84.4 (1F), −91.2 (1F), −210.0 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.26 (1H, m), 7.18 (1H, s), 7.53 (1H, s), 8.09 (1H,s) ppm

Example 5

Into a 50 ml autoclave was poured 6.71 g of pyrrole (100 mmol, meltingpoint of −23° C.), and evacuation and replacement of atmosphere in theautoclave with nitrogen gas were carried out three times at roomtemperature. After the inside of a system was evacuated,hexafluoropropylene (HFP) was introduced until the inside pressure ofthe system reached 0.1 MPa·G. Then the temperature of the reactionsystem was increased to 60° C., and HFP was further introduced tomaintain the inside pressure of the reaction system at 0.3 to 0.5 MPa·G.Supply of HFP was stopped when the amount of HFP reached 1.1 equivalents(17 g=110 mmol) to pyrrole, and stirring was continued at 100° C. Eighthours after starting of the stirring, the inside of the reaction systemwas brought to room temperature, followed by evacuation and thendistillation in such a state to obtain 18.0 g of distillate at 108° C.(yield: 83%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,3,3,3-hexafluoropropyl)pyrrole. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 94%.

¹⁹F-NMR (CD₃COCD₃): δ−74.2 (3F), −86.4 (1F), −89.5 (1F), −211.2 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.26 (1H, m), 6.24 (2H, m), 6.75 (2H, m) ppm

Example 6

Into a 50 ml autoclave was poured 6.81 g of pyrazole (100 mmol, meltingpoint of 67° C.), and evacuation and replacement of atmosphere in theautoclave with nitrogen gas were carried out three times at roomtemperature. After the inside of a system was evacuated,hexafluoropropylene (HFP) was introduced until the inside pressure ofthe system reached 0.1 MPa·G. Then the temperature of the reactionsystem was increased to 75° C., and HFP was further introduced tomaintain the inside pressure of the reaction system at 0.3 to 0.5 MPa·G.Supply of HFP was stopped when the amount of HFP reached 1.1 equivalents(17 g=110 mmol) to pyrazole, and stirring was continued at 100° C. Eighthours after starting of the stirring, the inside of the reaction systemwas brought to room temperature, followed by evacuation and thendistillation in such a state to obtain 19.2 g of distillate at 88° C./96mmHg (yield: 88%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,3,3,3-hexafluoropropyl)pyrazole. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 91%.

¹⁹F-NMR (CD₃COCD₃): δ−75.5 (3F), −83.8 (1F), −90.0 (1F), −214.2 (1F) ppm

¹-NMR (CD₃COCD₃): δ6.10 (1H, m), 6.26 (1H, m), 7.74 (2H, s) ppm

Example 7

Into a 50 ml autoclave was poured 6.91 g of 1,2,4-triazole (100 mmol,melting point of 120° C.), and evacuation and replacement of atmospherein the autoclave with nitrogen gas were carried out three times at roomtemperature. After the inside of a system was evacuated,hexafluoropropylene (HFP) was introduced until the inside pressure ofthe system reached 0.1 MPa·G. Then the temperature of the reactionsystem was increased to 135° C., and HFP was further introduced tomaintain the inside pressure of the reaction system at 0.3 to 0.5 MPa·G.Supply of HFP was stopped when the amount of HFP reached 1.1 equivalents(17 g=110 mmol) to 1,2,4-triazole, and stirring was continued at 100° C.Eight hours after starting of the stirring, the inside of the reactionsystem was brought to room temperature, followed by evacuation and thendistillation in such a state to obtain 17.5 g of distillate at 90° C./90mmHg (yield: 80%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,3,3,3-hexafluoropropyl)-1,2,4-triazole. To this crude reactionproduct was added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yieldby a ¹⁹F-NMR analysis based on ethyl trifluoroacetate was 87%.

¹⁹F-NMR (CD₃COCD₃): δ−72.6 (3F), −88.9 (1F), −93.4 (1F), −211.4 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.25 (1H, m), 8.09 (1H, s), 8.38 (1H, s) ppm

Example 8

Into a 50 ml autoclave were poured 8.21 g of 2-methylimidazole (100mmol, melting point of 142° C.) and tetrahydrofuran (3.0 ml) as amelting point depressor, and evacuation and replacement of atmosphere inthe autoclave with nitrogen gas were carried out three times at −78° C.After the inside of a system was evacuated, hexafluoropropylene (HFP)was introduced until the inside pressure of the system reached 0.1MPa·G. Then the temperature of the reaction system was increased to 100°C., and HFP was further introduced to maintain the inside pressure ofthe reaction system at 0.3 to 0.5 MPa·G. Supply of HFP was stopped whenthe amount of HFP reached 1.1 equivalents (17 g=110 mmol) to2-methylimidazole, and stirring was continued at 100° C. Eight hoursafter starting of the stirring, the inside of the reaction system wasbrought to room temperature, followed by evacuation and thendistillation in such a state to obtain 20.1 g of distillate at 78° C./24mmHg (yield: 86%).

According to a NMR analysis, it was confirmed that this product was2-methyl-1-(1,1,2,3,3,3-hexafluoropropyl)imidazole. To this crudereaction product was added 2.84 g (20 mmol) of ethyl trifluoroacetate,and yield by a ¹⁹F-NMR analysis based on ethyl trifluoroacetate was 96%.

¹⁹F-NMR (CD₃COCD₃): δ−73.9 (3F), −84.4 (1F), −91.2 (1F), −210.0 (1F) ppm

¹H-NMR (CD₃COCD₃): δ2.65 (3H, s), 6.26 (1H, m), 7.15 (1H, s), 7.50 (1H,s) ppm

Example 9

Into a 50 ml autoclave was poured 11.7 g of indole (100 mmol, meltingpoint of 52° C.), and evacuation and replacement of atmosphere in theautoclave with nitrogen gas were carried out three times at roomtemperature. After the inside of a system was evacuated,tetrafluoroethylene (TFE) was introduced until the inside pressure ofthe system reached 0.1 MPa·G. Then the temperature of the reactionsystem was increased to 60° C., and TFE was further introduced tomaintain the inside pressure of the reaction system at 0.3 to 0.5 MPa·G.Supply of TFE was stopped when the amount of TFE reached 1.1 equivalents(11 g=110 mmol) to indole, and stirring was continued at 60° C. Eighthours after starting of the stirring, the inside of the reaction systemwas brought to room temperature, followed by evacuation and thendistillation in such a state to obtain 16.0 g of distillate at 77°C./8.0 mmHg (yield: 74%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,2-tetrafluoroethyl)indole. To this crude reaction product wasadded 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a ¹⁹F-NMRanalysis based on ethyl trifluoroacetate was 87%.

¹⁹F-NMR (CD₃COCD₃): δ−98.1 (2F), −144.6 (2F) ppm

¹H-NMR (CD₃COCD₃): δ6.23 (1H, m), 6.52 (1H, s), 7.00-7.30 (4H, m), 7.65(1H, m) ppm

Example 10

Into a 50 ml autoclave were poured 12.0 g of purine (100 mmol, meltingpoint of 214° C.) and tetrahydrofuran (3.0 ml) as a melting pointdepressor, and the inside of the autoclave was cooled to −78° C., andevacuation and replacement of atmosphere in the autoclave with nitrogengas were carried out three times. After the inside of a system wasevacuated, tetrafluoroethylene (TFE) was introduced as a melting pointdepressor until the inside pressure of the system reached 0.1 MPa·G.Then the temperature of the reaction system was increased to 120° C.,and TFE was further introduced to maintain the inside pressure of thereaction system at 0.3 to 0.5 MPa·G. Supply of TFE was stopped when theamount of TFE reached 1.1 equivalents (11 g=110 mmol) to purine, andstirring was continued at 120° C. Eight hours after starting of thestirring, the inside of the reaction system was brought to roomtemperature, followed by evacuation, dissolution in ethanol andre-crystallization with hexane to obtain 13.6 g of a solid (yield: 62%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,2-tetrafluoroethyl)purine. To this crude reaction product wasadded 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a ¹⁹F-NMRanalysis based on ethyl trifluoroacetate was 77%.

¹⁹F-NMR (CD₃COCD₃): δ−93.6 (2F), −140.9 (2F) ppm

¹H-NMR (CD₃COCD₃): δ7.25 (1H, s), 8.70 (1H, s), 9.00 (1H, s), 9.21 (1H,s) ppm

Example 11

Into a 50 ml autoclave were poured 18.1 g of theophylline (100 mmol,melting point of 274° C.) which was a purine derivative, andtetrahydrofuran (5.0 ml) as a melting point depressor, and the inside ofthe autoclave was cooled to −78° C. and evacuation and replacement ofatmosphere in the autoclave with nitrogen gas were carried out threetimes. After the inside of a system was evacuated, tetrafluoroethylene(TFE) was introduced until the inside pressure of the system reached 0.1MPa·G. Then the temperature of the reaction system was increased to 120°C., and TFE was further introduced to maintain the inside pressure ofthe reaction system at 0.3 to 0.5 MPa·G. Supply of TFE was stopped whenthe amount of TFE reached 1.1 equivalents (11 g=110 mmol) totheophylline, and stirring was continued at 120° C. Eight hours afterstarting of the stirring, the inside of the reaction system was broughtto room temperature, followed by evacuation, dissolution in ethanol andre-crystallization with hexane to obtain 14.5 g of a solid (yield: 52%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,2-tetrafluoroethyl)theophylline. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 81%.

¹⁹F-NMR (DMSO-d₆): δ−95.8 (2F), −140.1 (2F) ppm

¹H-NMR (DMSO-d₆): δ3.24 (3H, s), 3.44 (3H, s), 7.30 (1H, m), 7.98 (1H,s) ppm

Example 12

Into a 50 ml autoclave was poured 21.2 g ofN-(t-butoxycarbonyl)histamine (100 mmol, melting point of 83° C.) whichwas an imidazole compound, and the inside of the autoclave was cooled to−78° C. and evacuation and replacement of atmosphere in the autoclavewith nitrogen gas were carried out three times. After the inside of asystem was evacuated, tetrafluoroethylene (TFE) was introduced until theinside pressure of the system reached 0.1 MPa·G. Then the temperature ofthe reaction system was increased to 90° C., and TFE was furtherintroduced to maintain the inside pressure of the reaction system at 0.3to 0.5 MPa·G. Supply of TFE was stopped when the amount of TFE reached1.1 equivalents (11 g=110 mmol) to N-(t-butoxycarbonyl)histamine, andstirring was continued at 90° C. Eight hours after starting of thestirring, the inside of the reaction system was brought to roomtemperature, followed by evacuation, dissolution in chloroform andre-crystallization with hexane to obtain 17.6 g of a solid (yield: 63%).

According to a NMR analysis, it was confirmed that this product wasN-(t-butoxycarbonyl)-N¹-(1,1,2,2-tetrafluoroethyl)histamine. To thiscrude reaction product was added 2.84 g (20 mmol) of ethyltrifluoroacetate, and yield by a ¹⁹F-NMR analysis based on ethyltrifluoroacetate was 91%.

¹⁹F-NMR (CD₃COCD₃): δ−100.4 (2F), −139.8 (2F) ppm

¹H-NMR (CD₃COCD₃): δ1.31 (9H, s), 2.70-3.10 (4H, m), 6.80 (1H, s), 7.27(1H, m), 7.54 (1H, s) ppm

Example 13

Into a 50 ml autoclave were poured 31.8 g (100 mmol) ofNα-(t-butoxycarbonyl)tryptophan methyl ester which was an indolecompound, and tetrahydrofuran (5.0 ml) as a melting point depressor, andthe inside of the autoclave was cooled to −78° C. and evacuation andreplacement of atmosphere in the autoclave with nitrogen gas werecarried out three times. After the inside of a system was evacuated,tetrafluoroethylene (TFE) was introduced until the inside pressure ofthe system reached 0.1 MPa·G. Then the temperature of the reactionsystem was increased to 120° C., and TFE was further introduced tomaintain the inside pressure of the reaction system at 0.3 to 0.5 MPa·G.Supply of TFE was stopped when the amount of TFE reached 1.1 equivalents(11 g=110 mmol) to purine, and stirring was continued at 120° C. Eighthours after starting of the stirring, the inside of the reaction systemwas brought to room temperature, followed by evacuation and refining ofa crude reaction product as it was with a developing solvent of hexaneand ethyl acetate of 4:1 by using silica gel chromatography to obtain34.6 g of a product (yield: 82%).

According to a NMR analysis, it was confirmed that this product wasNα-(t-butoxycarbonyl)-N¹-(1,1,2,2-tetrafluoroethyl)tryptophan methylester. To this crude reaction product was added 2.84 g (20 mmol) ofethyl trifluoroacetate, and yield by a ¹⁹F-NMR analysis based on ethyltrifluoroacetate was 87%.

¹⁹F-NMR (CD₃COCD₃): δ−102.4 (2F), −142.0 (2F) ppm

¹H-NMR (CD₃COCD₃): δ1.31 (9H, s), 2.80-3.80 (2H, m), 3.64 (3H, s),6.50-7.80 (6H, m) ppm

Example 14

Into a 50 ml autoclave was poured 6.81 g (100 mmol) of imidazole, andevacuation and replacement of atmosphere in the autoclave with nitrogengas were carried out three times at room temperature. After the insideof a system was evacuated, vinylidene fluoride was introduced until theinside pressure of the system reached 0.1 MPa·G. Then the temperature ofthe reaction system was increased to 100° C. which was higher than themelting point of imidazole, and perfluoro(methyl vinyl ether) (PMVE) wasintroduced to maintain the inside pressure of the reaction system at 0.3to 0.5 MPa·G. Supply of vinylidene fluoride was stopped when the amountof vinylidene fluoride reached 1.1 equivalents (7.1 g=110 mmol) toimidazole, and stirring was continued at 100° C. Eight hours afterstarting of the stirring, the inside of the reaction system was broughtto room temperature, followed by evacuation and then distillation insuch a state to obtain 11.9 g of distillate at 99° C. (yield: 90%).

According to a NMR analysis, it was confirmed that this product was1-(1,1-difluoroethyl)imidazole. To this crude reaction product was added2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a ¹⁹F-NMRanalysis based on ethyl trifluoroacetate was 94%.

¹⁹F-NMR (CD₃COCD₃): δ−93.2 (2F) ppm ¹H-NMR (CD₃COCD₃): δ1.96 (3H, t),7.15 (1H, s), 7.46 (1H, s), 8.01 (1H, s) ppm

Example 15

Into a 50 ml autoclave was poured 6.81 g (100 mmol) of imidazole, andevacuation and replacement of atmosphere in the autoclave with nitrogengas were carried out three times at room temperature. After the insideof a system was replaced by nitrogen gas atmosphere, the insidetemperature of the autoclave was raised to 100° C. and 33.0 g (110 mmol)of perfluoro-2-methyl-2-pentene was introduced over one hour underpressurized nitrogen gas atmosphere. After stirring at 100° C. for eighthours, the inside of the reaction system was brought to roomtemperature, followed by evacuation and then distillation in such astate to obtain 24.7 g of distillate at 76° C./4.0 mmHg (yield: 67%).

According to a NMR analysis, it was confirmed that this product was1-(2H-perfluoro-1-ethyl-2-methylpropyl)imidazole. To this crude reactionproduct was added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yieldby a ¹⁹F-NMR analysis based on ethyl trifluoroacetate was 75%.

¹⁹F-NMR (CD₃COCD₃): δ−72.9 (3F), −71.8 (3F), −78.9 (3F), −121.7 (2F),−139.7 (1F, m) ppm

¹H-NMR (CD₃COCD₃): δ3.86 (1H, m), 7.15 (1H, s), 7.46 (1H, s), 8.01 (1H,s) ppm

Example 16

Into a 50 ml autoclave was poured 6.81 g (100 mmol) of imidazole, andevacuation and replacement of atmosphere in the autoclave with nitrogengas were carried out three times at room temperature. After the insideof a system was evacuated, perfluoro(methyl vinyl ether) (PMVE) wasintroduced until the inside pressure of the system reached 0.1 MPa·G.Then the temperature of the reaction system was increased to 100° C.which was higher than the melting point of imidazole, and PMVE wasfurther introduced to maintain the inside pressure of the reactionsystem at 0.3 to 0.5 MPa·G. Supply of PMVE was stopped when the amountof PMVE reached 1.1 equivalents (18 g=110 mmol) to imidazole, andstirring was continued at 100° C. Eight hours after starting of thestirring, the inside of the reaction system was brought to roomtemperature, followed by evacuation and then distillation in such astate to obtain 18.5 g of distillate at 76° C./83 mmHg (yield: 79%).

According to a NMR analysis, it was confirmed that this product was1-(1,1,2-trifluoro-2-trifluoromethoxyethyl)imidazole. To this crudereaction product was added 2.84 g (20 mmol) of ethyl trifluoroacetate,and yield by a ¹⁹F-NMR analysis based on ethyl trifluoroacetate was 83%.

¹⁹F-NMR (CD₃COCD₃): δ−58.6 (3F), −93.4 (1F), −95.0 (1F), −144.0 (1F) ppm

¹H-NMR (CD₃COCD₃): δ7.09 (1H, dt), 7.18 (1H, s), 7.49 (1H, s), 8.04 (1H,s) ppm

Example 17

Into a 50 ml three-necked flask was poured 6.81 g (100 mmol) ofimidazole, and evacuation and replacement of atmosphere in the flaskwith nitrogen gas were carried out three times at room temperature.After the inside of a system was replaced by nitrogen gas atmosphere,43.2 g (100 mmol) of perfluoro vinyl ether:

CF₂═CFOCF₂CF(CF₃)OC₃F₇

(N2VE) was added dropwise at 90° C. over one hour, and the insidetemperature of the reaction system was increased to 100° C., andstirring was continued. Eight hours after starting of the stirring, theinside of the reaction system was brought to room temperature, followedby distillation in such a state to obtain 40.0 g of distillate at 90°C./2.3 mmHg (yield: 80%).

According to a NMR analysis, it was confirmed that this product was1-(2H-perfluoro-3,6-dioxa-5-methylnonyl)imidazole:

Im-CF₂CHFOCF₂CF(CF₃)OC₃F₇

wherein Im represents an imidazole ring. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 81%.

¹⁹F-NMR (CD₃COCD₃): δ−78.5-−81.5 (10F), −92.3-96.3 (2F), −128.7 (2F),−143.2-−144.0 (3F) ppm

¹H-NMR (CD₃COCD₃): δ7.07-7.25 (1H, m), 7.17 (1H, s), 7.44 (1H, s), 7.99(1H, s) ppm

Example 18

Into a 50 ml three-necked flask was poured 6.81 g (100 mmol) ofimidazole, and evacuation and replacement of atmosphere in the flaskwith nitrogen gas were carried out three times at room temperature.After the inside of a system was replaced by nitrogen gas atmosphere,34.9 g (100 mmol) of fluorinated vinyl ether:

CF₂═CFOCF₂CF₂CFClCF₂Cl

was added dropwise at 90° C. over one hour, and the inside temperatureof the reaction system was increased to 100° C., and stirring wascontinued. Eight hours after starting of the stirring, the inside of thereaction system was brought to room temperature, followed bydistillation in such a state to obtain 32.1 g of distillate at 83°C./3.4 mmHg (yield: 77%).

According to a NMR analysis, it was confirmed that this product was1-(2H-perfluoro-6,7-dichloro-3-oxaheptyl)imidazole:

Im-CF₂CHFOCF₂CF₂CFClCF₂Cl

wherein Im represents an imidazole ring. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 80%.

¹⁹F-NMR (CD₃COCD₃): δ−63.7 (2F), −82.2 (2F), −93.8 (1F), −95.4 (1F),−117.3 (2F), −130.8 (1F), −145.7 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.73 (1H, dt, J=52.8, 5.0 Hz), 7.19 (1H, s), 7.48(1H, s), 8.04 (1H, s) ppm

Example 19

Into a 50 ml three-necked flask were poured 6.83 g (100 mmol) of zincand dioxane (20 g), followed by activation with dibromoethane undernitrogen gas atmosphere. The inside temperature of a system wasincreased to 100° C., and 20.9 g (50 mmol) of1-(2H-perfluoro-6,7-dichloro-3-oxaheptyl)imidazole:

Im-CF₂CHFOCF₂CF₂CFClCF₂Cl

wherein Im represents an imidazole ring, was added dropwise over thirtyminutes. After stirring at 100° C. for eight hours, the inside of thereaction system was brought to room temperature, followed by filtrationof a reaction solution with sellaite and then distillation in such astate to obtain 12.3 g of distillate at 76° C./11 mmHg (yield: 71%).

According to a NMR analysis, it was confirmed that this product was1-(2H-perfluoro-3-oxa-6-heptenyl)imidazole:

Im-CF₂CHFOCF₂CF₂CF═CF₂

wherein Im represents an imidazole ring.

¹⁹F-NMR (CD₃COCD₃): δ−80.9 (2F), −91.8 (1F), −93.1 (1F), −95.5 (1F),−107.4 (1F), −121.6 (2F), −143.5 (1F), −190.8 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.59 (1H, dt, J=52.2, 5.0 Hz), 7.20 (1H, s), 7.46(1H, s), 8.02 (1H, s) ppm

Example 20

Into a 50 ml three-necked flask was poured 6.81 g (100 mmol) ofimidazole, and evacuation and replacement of atmosphere in the flaskwith nitrogen gas were carried out three times at room temperature.After the inside of a system was replaced by nitrogen gas atmosphere,35.6 g (100 mmol) of fluorinated vinyl ether:

CF₂═CFCF₂CF₂OCF(CF₃)COOCH₃

was added dropwise at 90° C. over one hour, and the inside temperatureof the reaction system was increased to 100° C., and stirring wascontinued. Eight hours after starting of the stirring, the inside of thereaction system was brought to room temperature, followed by evacuationand refining of a crude reaction product as it was with a developingsolvent of hexane and ethyl acetate of 10:1 by using silica gelchromatography to obtain 37.7 g of a product (yield: 89%).

According to a NMR analysis, it was confirmed that this was methylproduct 7-(1-imidazolyl)-6H-perfluoro-2-methyl-3-oxaheptanoate:

Im-CF₂CHFCF₂CF₂OCF(CF₃)COOCH₃

wherein Im represents an imidazole ring. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 90%.

¹⁹F-NMR (CD₃COCD₃): δ−72.8 (2F), −82.4 (3F), −87.4 (1F), −93.4 (1F),−114.3 (2F), −133.0 (1F), −207.8 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.38 (1H, s), 6.32 (1H, m), 7.19 (1H, s), 7.52 (1H,s), 8.09 (1H, s) ppm

Example 21

Into a 100 ml three-necked flask were poured 21.2 g (50 mmol) of methyl7-(1-imidazolyl)-6H-perfluoro-2-methyl-3-oxaheptanoate and 50 g ofmethanol, and thereto was added dropwise 50 ml of 1N aqueous solution ofsodium hydroxide, followed by stirring at room temperature for 24 hours.Then after evacuating the inside of a system and removing the solvent,the inside temperature was elevated to 60° C., followed by 24-hourdrying to obtain a solid of carboxylate.

Into a 50 ml three-necked flask equipped with a distillation column werepoured the carboxylate and 20 g of tetraglyme. The inside temperaturewas increased to 200° C. under reduced pressure of 30 mmHg, and aproduced liquid was taken out. The obtained crude reaction product wassubjected to distillation as it was, and 7.61 g of distillate at 71°C./12 mmHg was obtained (yield: 44%).

According to a NMR analysis, it was confirmed that this product was1-(2H-perfluoro-5-oxa-6-heptenyl)imidazole:

Im-CF₂CHFCF₂CF₂OCF═CF₂

wherein Im represents an imidazole ring.

¹⁹F-NMR (CD₃COCD₃): δ−76.4 (2F), −86.2 (1F), −92.0 (1F), −112.9 (1F),−115.6 (2F), −121.2 (1F), −135.8 (1F), −210.8 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.25 (1H, m), 7.19 (1H, s), 7.52 (1H, s), 8.03 (1H,s) ppm

Example 22

Into a 50 ml three-necked flask was poured 6.81 g (100 mmol) ofimidazole, and evacuation and replacement of atmosphere in the flaskwith nitrogen gas were carried out three times at room temperature.After the inside of a system was replaced by nitrogen gas atmosphere,35.8 g (100 mmol) of fluorinated vinyl ether:

CF₂═CFOCF₂CF(CF₃)OCF₂CF═CH₂

was added dropwise at 90° C. over one hour, and the inside temperatureof the reaction system was increased to 100° C., and stirring wascontinued. Eight hours after starting of the stirring, the inside of thereaction system was brought to room temperature, followed bydistillation in such a state to obtain 33.2 g of distillate at 90°C./2.6 mmHg (yield: 78%).

According to a NMR analysis, it was confirmed that this product was1-(2H,9H,9H-perfluoro-3,6-dioxa-5-methyl-8-nonenyl)imidazole:

Im-CF₂CHFOCF₂CF(CF₃)OCF₂CF═CH₂

wherein Im represents an imidazole ring. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 81%.

¹⁹F-NMR (CD₃COCD₃): δ−72.2 (2F), −78.3 (3F), −82.4-−84.5 (2F),−92.0-−94.5 (2F), −123.5 (1F), −143.2 (1F), −144.4 (1F) ppm

¹H-NMR (CD₃COCD₃): δ5.34-5.59 (2H, m), 7.05-7.20 (1H, m), 7.16 (1H, s),7.43 (1H, s), 8.00 (1H, s) ppm

Example 23

Into a 50 ml autoclave was poured 6.81 g (100 mmol) of imidazole, andevacuation and replacement of atmosphere in the autoclave with nitrogengas were carried out three times at room temperature. After the insideof a system was replaced by nitrogen gas atmosphere, the insidetemperature was elevated to 100° C., and 12.5 g (45 mmol) ofperfluorobutenyl vinyl ether:

CF₂═CFOCF₂CF₂CF═CF₂

was introduced over one hour under pressurized nitrogen gas atmosphere,and after stirring at 100° C. for eight hours, the inside of thereaction system was brought to room temperature, followed by refining ofa crude reaction product as it was with a developing solvent of hexaneand ethyl acetate of 6:1 by using silica gel chromatography to obtain14.0 g of a product (yield based on perfluorobutenyl vinyl ether: 75%).

According to a NMR analysis, it was confirmed that this product was2-(1-imidazolyl)-1,2,2-trifluoroethyl=4-(1-imidazolyl)-1,1,2,2,3,4,4-heptafluorobutyl=ether:

Im-CF₂CHFOCF₂CF₂CHFCF₂-Im

wherein Im represents an imidazole ring. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 78%.

¹⁹F-NMR (CD₃COCD₃): δ−82.2 (2F), −86.4 (1F), −90.4 (1F), −92.5 (1F),−96.4 (1F), −118 (2F), −138.0 (1F), −203.9 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.05-6.26 (1H, m), 6.98-7.09 (1H, m), 7.18 (1H, s),7.50 (1H, s), 8.06 (1H, s) ppm

Example 24

Into a 100 ml three-necked flask was poured 6.81 g (100 mmol) ofimidazole, and evacuation and replacement of atmosphere in the flaskwith nitrogen gas were carried out three times at room temperature.After the inside of a system was replaced by nitrogen gas atmosphere,the inside temperature was elevated to 90° C., and a solution preparedby adding 50 ml of diglyme to 59.0 g (100 mmol) of tetrafluoroethyleneoligomer:

CF₂═CH—(CF₂)₈—I

was added dropwise over one hour. After the addition, the temperature ofthe reaction system was elevated to 100° C. and stirring was continued.Eight hours after starting of the stirring, the inside of the reactionsystem was brought to room temperature. The crude reaction product wassubjected to refining as it was with a developing solvent of hexane andethyl acetate of 8:1 by using silica gel chromatography to obtain 56.1 gof a product (yield: 85%).

According to a NMR analysis, it was confirmed that this product was1-(2H,2H-perfluoro-10-iododecyl)imidazole:

Im-CF₂CH₂—(CF₂)₈—I

wherein Im represents an imidazole ring. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 79%.

¹⁹F-NMR (CD₃COCD₃): δ−54.6 (2F), −94.2 (2F), −114.5 (2F), −122.0 (2F),−122.3 (4F), −123.2 (2F), −124.2 (2F), −126.7 (2F) ppm

¹H-NMR (CD₃COCD₃): δ4.32 (2H, m), 7.20 (1H, s), 7.46 (1H, s), 8.02 (1H,s) ppm

Example 25

Into a 100 ml three-necked flask was poured 7.49 g (110 mmol) ofimidazole, and evacuation and replacement of atmosphere in the flaskwith nitrogen gas were carried out three times at room temperature.After the inside of a system was replaced by nitrogen gas atmosphere,the inside temperature was elevated to 90° C., and a solution preparedby adding 50 ml of diglyme to 31.3 g (50 mmol) of tetrafluoroethyleneoligomer:

CF₂═CH—(CF₂)₈—CH═CF₂

was added dropwise over one hour. After the addition, the temperature ofthe reaction system was elevated to 100° C. and stirring was continued.Eight hours after starting of the stirring, the inside of the reactionsystem was brought to room temperature. The crude reaction product wassubjected to refining as it was with a developing solvent of hexane andethyl acetate of 3:1 by using silica gel chromatography to obtain 23.6 gof a product (yield based on a diene compound: 71%).

According to a NMR analysis, it was confirmed that this product was1,12-bis(1-imidazolyl)-2H,2H,11H,11H-perfluorododecane:

Im-CF₂CH₂—(CF₂)₈—CH₂CF₂-Im

wherein Im represents an imidazole ring. To this crude reaction productwas added 2.84 g (20 mmol) of ethyl trifluoroacetate, and yield by a¹⁹F-NMR analysis based on ethyl trifluoroacetate was 68%.

¹⁹F-NMR (CD₃COCD₃): δ−92.9 (4F), −119.4 (4F), −122.7 (4F), −123.7 (4F),−124.2 (4F) ppm

¹H-NMR (CD₃COCD₃): δ4.28 (4H, m), 7.22 (2H, s), 7.46 (2H, s), 8.01 (2H,s) ppm

Example 26

Into a 100 ml three-necked flask were poured 1.36 g (20 mmol) ofimidazole and 25 ml of diglyme, and evacuation and replacement ofatmosphere in the flask with nitrogen gas were carried out three timesat room temperature. After the inside of a system was replaced bynitrogen gas atmosphere, the inside temperature was elevated to 60° C.,and a solution prepared by adding 25 ml of diglyme to 15.0 g ofvinylidene fluoride polymer:

CF₂═CH—(CF₂CH₂)_(21.4)—CF₃

(Mn=1,500, —CH═CF₂ end: 63% by mole) was added dropwise over one hour.After the addition, stirring of the reaction system was continued at thetemperature of 60° C. Eight hours after starting of the stirring, theinside of the reaction system was brought to room temperature. Thereaction solution was poured into hexane and a precipitated product wasfiltrated and subjected to vacuum drying at 60° C. to obtain 13.6 g of apolymer.

According to a NMR analysis, it was confirmed that —CH═CF₂ end (¹⁹F-NMR:δ−72-−73 ppm (—CH═CF ₂), ¹H-NMR: δ4.7 ppm (—CH═CF₂)) had been completelyconsumed and this polymer was a vinylidene fluoride polymer having animidazolyl group:

Im-CF₂CH₂—(CF₂CH₂)_(21.4)—CF₃ (Mn=1,540)

wherein Im represents an imidazole ring.

¹⁹F-NMR (CD₃COCD₃): δ−60.4, —90-−115, −95.9 ppm

¹H-NMR (CD₃COCD₃): δ2.70-4.00, 7.20, 7.45, 8.00 ppm

Example 27

Into a 100 ml three-necked flask were poured 2.72 g (40 mmol) ofimidazole and 25 ml of diglyme, and evacuation and replacement ofatmosphere in the flask with nitrogen gas were carried out three timesat room temperature. After the inside of a system was replaced bynitrogen gas atmosphere, the inside temperature was elevated to 60° C.,and a solution prepared by adding 25 ml of diglyme to 17.0 g ofvinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer:

CF₂═CH—(CF₂CH₂)_(12.8)[CF₂CF(CF₃)]_(2.3)(CF₂CF₂)_(4.1)—CH═CF₂

(Mn=1,700, —CH═CF₂ end: 79% by mole) was added dropwise over one hour.After the addition, stirring was continued at the temperature of thereaction system of 60° C. Eight hours after starting of the stirring,the inside of the reaction system was brought to room temperature. Thereaction solution was poured into hexane and a precipitated product wasfiltrated and subjected to vacuum drying at 60° C. to obtain 16.3 g of apolymer.

According to a NMR analysis, it was confirmed that —CH═CF₂ end (¹⁹F-NMR:δ−72-−73 ppm (—CH═CF ₂), ¹H-NMR: 4.7 ppm (—CH═CF₂)) had been completelyconsumed and this polymer was a vinylidenefluoride/hexafluoropropylene/tetrafluoroethylene copolymer having animidazolyl group:

Im-CF₂CH₂—(CF₂CH₂)_(12.8)[CF₂CF(CF₃)]_(2.3)(CF₂CF₂)_(4.1)—CH₂CF₂-Im(Mn=1,800)

wherein Im represents an imidazole ring.

¹⁹F-NMR (CD₃COCD₃): δ−70.2, −90.0-−95.0, −96.2, −108.0-−115.0,−120.0-−123.0, −182.0 ppm

¹H-NMR (CD₃COCD₃): δ2.70-4.00, 7.20, 7.45, 8.00 ppm

Example 28

Into a 30 ml three-necked flask was poured 5.00 g (29.7 mmol) of1-(1,1,2,2-tetrafluoroethyl)imidazole synthesized in Example 1, andthereto was added dropwise 1.10 equivalents (5.36 g=32.7 mmol) of methyltrifluoromethanesulfonate (Me-OTf) at a temperature not exceeding 30° C.on ice bath under nitrogen gas atmosphere. After the addition, stirringwas continued in such a state for one hour, and then a 6-hour reactionwas continued at room temperature. Thereafter the inside of the systemwas evacuated and the inside temperature was elevated to 100° C.,followed by 6-hour drying to obtain 9.31 g of a product (yield: 94%).

According to a NMR analysis, it was confirmed that this product was1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazoliumtrifluoromethanesulfonate. The obtained product was a solid at roomtemperature.

¹⁹F-NMR (CD₃COCD₃): δ−77.6 (3F), −98.7 (2F), −136.4 (2F) ppm

¹H-NMR (CD₃COCD₃): δ4.21 (3H, s), 7.06 (1H, tt), 8.09 (1H, s), 8.19 (1H,s), 9.83 (1H, s) ppm

Example 29

8.49 g of 1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazoliumtrifluoromethanesulfonate was prepared (yield: 97%) in the same manneras in Example 28 except that 5.00 g (22.9 mmol) of1-(1,1,2,3,3,3-hexafluoropropyl)imidazole synthesized in Example 4 wasused instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole. The obtainedproduct was a solid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−73.4 (3F), −74.5 (3F), −87.7 (1F), −93.5 (1F),−210.0 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.24 (3H, s), 6.52 (1H, m), 8.09 (1H, s), 8.26 (1H,s), 9.82 (1H, s) ppm

Example 30

8.31 g of1-methyl-3-(1,1,2-trifluoro-2-trifluoromethoxyethyl)imidazoliumtrifluoromethanesulfonate was prepared (yield: 98%) in the same manneras in Example 28 except that 5.00 g (21.4 mmol) of1-(1,1,2-trifluoro-2-trifluoromethoxyethyl)imidazole synthesized inExample 16 was used instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole.The obtained product was a solid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−58.5 (3F), −77.1 (3F), −95.9 (1F), −97.8 (1F),−144.1 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.21 (3H, s), 7.30 (1H, d), 8.08 (1H, s), 8.20 (1H,s), 9.77 (1H, s) ppm

Example 31

6.38 g of 1-methyl-3-(2H-perfluoro-3,6-dioxa-5-methylnonyl)imidazoliumtrifluoromethanesulfonate was prepared (yield: 96%) in the same manneras in Example 28 except that 5.00 g (10.0 mmol) of1-(2H-perfluoro-3,6-dioxa-5-methylnonyl)imidazole synthesized in Example17 was used instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole. Theobtained product was a highly viscous liquid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−78.5-−81.5 (13F), −92.3-−96.3 (2F), −128.0 (2F),−143.2-−144.0 (3F) ppm

¹H-NMR (CD₃COCD₃): δ7.48 (1H, dd), 8.11 (1H, s), 8.18 (1H, s), 9.82 (1H,s) ppm

Example 32

6.83 g of 1-methyl-3-(2H-perfluoro-6,7-dichloro-3-oxaheptyl)imidazoliumtrifluoromethanesulfonate was prepared (yield: 98%) in the same manneras in Example 28 except that 5.00 g (12.0 mmol) of1-(2H-perfluoro-6,7-dichloro-3-oxaheptyl)imidazole synthesized inExample 18 was used instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole.The obtained product was a solid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−73.4 (3F), −62.3 (2F), −80.0 (2F) −92.2 (1F),−94.6 (1F), −115.9 (2F), −128.7 (1F), −145.3 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.21 (3H, s), 7.01 (1H, dt), 7.19 (1H, s), 7.48 (1H,s), 8.04 (1H, s), 8.10 (1H, s), 8.21 (1H, s), 9.80 (1H, s) ppm

Example 33

6.84 g of 1-methyl-3-(2H-perfluoro-3-oxa-6-heptenyl)imidazoliumtrifluoromethanesulfonate was prepared (yield: 93%) in the same manneras in Example 28 except that 5.00 g (14.4 mmol) of1-(2H-perfluoro-3-oxa-6-heptenyl)imidazole synthesized in Example 19 wasused instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole. The obtainedproduct was a solid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−76.1 (3F), −79.4 (2F), −90.2 (1F), −92.3 (1F),−94.2 (1F), −106.9 (1F), −120.2 (2F), −143.3 (1F), −190.7 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.18 (3H, s), 6.36 (1H, dt), 8.10 (1H, s), 8.21 (1H,s), 9.80 (1H, s) ppm

Example 34

6.89 g of 1-methyl-3-(2H-perfluoro-5-oxa-6-heptenyl)imidazoliumtrifluoromethanesulfonate was prepared (yield: 94%) in the same manneras in Example 28 except that 5.00 g (14.4 mmol) of1-(2H-perfluoro-5-oxa-6-heptenyl)imidazole synthesized in Example 21 wasused instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole. The obtainedproduct was a solid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−74.5 (3F), −77.8 (2F), −83.7 (1F), −90.9 (1F),−111.2 (1F), −115.0 (2F), −120.9 (1F), −135.7 (1F), −211.2 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.20 (3H, s), 6.41 (1H, m), 8.08 (1H, s), 8.19 (1H,s), 9.71 (1H, s) ppm

Example 35

6.56 g of1-methyl-3-(2H,9H,9H-perfluoro-3,6-dioxa-5-methyl-8-nonenyl)imidazoliumtrifluoromethanesulfonate was prepared (yield: 95%) in the same manneras in Example 28 except that 5.00 g (11.7 mmol) of1-(2H,9H,9H-perfluoro-3,6-dioxa-5-methyl-8-nonenyl)imidazole:Im-CF₂CHFOCF₂CF(CF₃)OCF₂CF═CH₂ synthesized in Example 22 was usedinstead of 1-(1,1,2,2-tetrafluoroethyl)imidazole. The obtained productwas a highly viscous liquid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−72.2 (2F), −77.5 (3F), −78.8 (3F), −82.9 (2F),−95.2 (1F), −99.1 (1F), −123.7 (1F), −143.3 (1F), −144.3 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.21 (3H, s), 5.42-5.61 (2H, m), 7.36-7.58 (1H, m),8.12 (1H, s), 8.17 (1H, s), 9.83 (1H, s) ppm

Example 36

5.35 g of 1-methyl-3-(2H,2H-perfluoro-10-iododecyl)imidazoliumtrifluoromethanesulfonate was prepared (yield: 86%) in the same manneras in Example 28 except that 5.00 g (7.60 mmol) of1-(2H,2H-perfluoro-10-iododecyl)imidazole synthesized in Example 24 wasused instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole and THF was usedas a solvent. The obtained product was a solid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−54.8 (2F), −74.1 (3F), −94.3 (2F), −114.4 (2F),−121.9 (2F), −122.3 (4F), −123.2 (2F), −123.9 (2F), −126.8 (2F) ppm

¹H-NMR (CD₃COCD₃): δ4.21 (3H, s), 4.48 (2H, m), 8.10 (1H, s), 8.22 (1H,s), 9.79 (1H, s) ppm

Example 37

Preparation was carried out in the same manner as in Example 28 exceptthat 5.00 g (7.55 mmol) of1,12-bis(1-imidazolyl)-2H,2H,11H,11H-perfluorododecane synthesized inExample 25 was used instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole,THF was used as a solvent, and 2.2 equivalents of methyltrifluoromethanesulfonate was used. Thus 6.89 g of a compound, in whichthe first position and the twelfth position of 2H,2H, 11H,11H-perfluorotetradecane were 1-methylimidazoliumtrifluoromethanesulfonate, was prepared (yield: 92%). The obtainedproduct was a solid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−74.8 (6F), −90.8 (4F), −119.3 (4F), −122.5 (4F),−123.7 (4F), −124.3 (4F) ppm

¹H-NMR (CD₃COCD₃): δ4.20 (6H, s), 4.53 (4H, m), 8.11 (2H, s), 8.27 (2H,s), 9.77 (2H, s) ppm

Example 38

5.20 g of a vinylidene fluoride polymer (Mn=1,630) comprising1-methylimidazolium trifluoromethanesulfonate was prepared in the samemanner as in Example 28 except that 5.00 g of vinylidene fluoridepolymer (Mn=1,540) having 63% by mole of imidazolyl group at its end andsynthesized in Example 26 was used instead of1-(1,1,2,2-tetrafluoroethyl)imidazole, and THF was used as a solvent.The obtained product was a solid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−60.6, −75.3, −89.0-−115.0, −98.9 ppm

¹H-NMR (CD₃COCD₃): δ2.70-4.00, 4.20, 4.81, 8.08, 8.26, 9.82 ppm

Example 39

5.63 g of a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylenecopolymer (Mn=2,050) comprising 1-methylimidazoliumtrifluoromethanesulfonate at both ends thereof was prepared in the samemanner as in Example 28 except that 5.00 g of the vinylidenefluoride/hexafluoropropylene/tetrafluoroethylene copolymer (Mn=1,800)having 79% by mole of imidazolyl group at its end and synthesized inExample 27 was used instead of 1-(1,1,2,2-tetrafluoroethyl)imidazole,and THF was used as a solvent. The obtained product was a solid at roomtemperature.

¹⁹F-NMR (CD₃COCD₃): δ−70.3, −73.8, −90-−95, −96, −108.0-−115.0,−120-−123, −182.0 ppm

¹H-NMR (CD₃COCD₃): δ2.70-4.00, 4.20, 4.79, 8.10, 8.25, 9.77 ppm

Example 40

Into a 50 ml three-necked autoclave were poured 10.0 g (59.4 mmol) of1-(1,1,2,2-tetrafluoroethyl)imidazole prepared in Example 1 and 20 ml ofdichloromethane, and evacuation and replacement of atmosphere in theautoclave with nitrogen gas were carried out three times on dryice/acetone bath. After the inside of the system was evacuated, 8.46 g(89.2 mmol) of methyl bromide was added thereto. After the addition, a6-hour reaction was carried out at 60° C. Thereafter the inside of thesystem was evacuated and the inside temperature was elevated to 100° C.,followed by 6-hour drying to obtain 13.7 g of a product (yield: 88%).The obtained product was a solid at room temperature.

According to a NMR analysis, it was confirmed that this product was1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazolium bromide.

¹⁹F-NMR (CD₃COCD₃): δ−96.5 (2F), −134.1 (2F) ppm

¹H-NMR (CD₃COCD₃): δ4.17 (3H, s), 7.04 (1H, tt), 8.10 (1H, s), 8.21 (1H,s), 9.80 (1H, s) ppm

Example 41

Into a 50 ml three-necked autoclave were poured 10.0 g (45.9 mmol) of1-(1,1,2,3,3,3-hexafluoropropyl)imidazole prepared in Example 4 and 20ml of dichloromethane, and evacuation and replacement of atmosphere inthe autoclave with nitrogen gas were carried out three times on dryice/acetone bath. After the inside of the system was evacuated, 6.53 g(68.8 mmol) of methyl bromide was added thereto. After the addition, a6-hour reaction was carried out at 60° C. Thereafter the inside of thesystem was evacuated and the inside temperature was elevated to 100° C.,followed by 6-hour drying to obtain 12.9 g of a product (yield: 90%).The obtained product was a solid at room temperature.

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium bromide.

¹⁹F-NMR (CD₃COCD₃): δ−75.1 (3F), −88.9 (1F), −92.0 (1F), −210.3 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.51 (1H, m), 8.12 (1H, s), 8.27 (1H, s), 9.91 (1H,s) ppm

Example 42

Into a 50 ml two-necked flask were poured 2.50 g (9.50 mmol) of1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazolium bromide synthesized inExample 40 and 20 ml of dichloromethane, and thereto was added dropwisea solution prepared by dissolving 6.60 g (9.50 mmol) of silvercarboxylate containing perfluoro polyether:

CH₂═CFCF₂OCF(CF₃)CF₂OCF(CF₃)CF₂OCF(CF₃)COOAg

in 20 ml of dichloromethane. After the addition, stirring was continuedfor one hour in such a state, and then the reaction solution wasfiltrated with sellaite and the temperature was elevated to 80° C. underreduced pressure, followed by 6-hour drying to obtain 7.17 g of aproduct (yield: 98%). The obtained product was a highly viscous liquidat room temperature.

According to a NMR analysis, it was confirmed that this product was1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazolium 12H,12H-perfluoro-2,5,8-trimethyl-3,6,9-trioxa-11-dodecenoate.

¹⁹F-NMR (CD₃COCD₃): δ−72.6 (2F), 87.5-85.0 (13F), −96.5 (2F), −113.6(1F), −123.2 (1F), −133.5 (2F), −144.3 (2F) ppm

¹H-NMR (CD₃COCD₃): δ4.21 (3H, s), 5.42-5.62 (2H, m), 7.10 (1H, tt), 8.10(1H, s), 8.19 (1H, s), 10.00 (1H, s) ppm

Example 43

5.88 g of 1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazoliumperfluoro-3,6-dioxa-4-methyl-7-octenesulfonate was prepared (yield: 99%)in the same manner as in Example 42 by using 2.50 g (9.50 mmol) of1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazolium bromide and 20 ml ofdichloromethane except that 5.23 g (9.50 mmol) of silver sulfonatecontaining perfluoro polyether:

CF₂═CFOCF₂CF(CF₃)OCF₂CF₂SO₃Ag

was used. The obtained product was a highly viscous liquid at roomtemperature.

¹⁹F-NMR (CD₃COCD₃): δ−80.0-−87.0 (7F), −95.5 (2F), −113.3 (2F), −114.2(1F), −122.8 (1F), −133.9 (2F), −136.8 (1F), −146.0 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.18 (3H, s), 7.11 (1H, tt), 8.10 (1H, s), 8.20 (1H,s), 9.91 (1H, s) ppm

Example 44

Into a 50 ml two-necked flask were poured 1.71 g of poly(sodiummethacrylate):

[CH₂CH(COONa)—]_(n)

(weight average molecular weight: 6,500) and 20 ml of water, and theretowas added dropwise 5.00 g (19.0 mmol) of1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazolium bromide. After theaddition, a polymer was precipitated. The precipitated polymer waswashed with water, followed by 8-hour vacuum drying at 60° C. to obtain5.02 g of a polymer.

According to a NMR analysis, it was confirmed that this polymer waspoly[1-methyl-3-(1,1,2,2-tetrafluoroethyl)imidazolium methacrylate]having a polymer side chain converted to imidazolium cation.

¹⁹F-NMR (CD₃COCD₃): δ−94.8 (2F), −134.7 (2F) ppm

¹H-NMR (CD₃COCD₃): δ1.30-1.55 (3H), 1.95-2.45 (2H), 3.97 (3H), 6.95-7.00(1H), 8.10 (1H, s), 8.20 (1H), 10.0 (1H) ppm

Example 45

Into a 50 ml two-necked flask were poured 6.18 g (10.5 mmol) ofcarboxylic acid containing perfluoro polyether:

CH₂═CFCF₂OCF(CF₃)CF₂OCF(CF₃)CF₂OCF(CF₃)COOH

and 20 ml of tetrahydrofuran, and thereto was added dropwise 1.95 g(11.6 mmol) of 1-(1,1,2,2-tetrafluoroethyl)imidazole. After theaddition, one-hour stirring was carried out in such a state, and thenthe temperature was elevated to 80° C. under reduced pressure, followedby 6-hour drying to obtain 7.77 g of a product (yield based oncarboxylic acid: 98%). The obtained product was a highly viscous liquidat room temperature.

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,2-tetrafluoroethyl)imidazolium12H,12H-perfluoro-2,5,8-trimethyl-3,6,9-trioxa-11-dodecenoate.

¹⁹F-NMR (CD₃COCD₃): δ−72.4 (2F), 87.5-85.0 (13F), −96.2 (2F), −113.8(1F), −122.9 (1F), −133.2 (2F), −143.6 (2F) ppm

¹H-NMR (CD₃COCD₃): δ1.60 (1H), 5.42-5.62 (2H, m), 6.99 (1H, m), 8.10(1H, s), 8.20 (1H, s), 9.82 (1H, s) ppm

Example 46

6.31 g of 1-(1,1,2,2-tetrafluoroethyl)imidazoliumperfluoro-3,6-dioxa-4-methyl-7-octenesulfonate was prepared (yield: 98%)in the same manner as in Example 44 by using 4.66 g (10.5 mmol) ofsulfonic acid containing perfluoro polyether:

CF₂═CFOCF₂CF(CF₃)OCF₂CF₂SO₃H

and 1.95 g (11.6 mmol) of 1-(1,1,2,2-tetrafluoroethyl)imidazole. Theobtained product was a highly viscous liquid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−80.0-−87.0 (7F), −94.9 (2F), −113.0 (2F), −113.9(1F), −122.9 (1F), −133.6 (2F), −137.2 (1F), −145.0 (1F) ppm

¹H-NMR (CD₃COCD₃): δ1.60 (1H), 7.07 (1H, tt), 8.08 (1H, s), 8.21 (1H,s), 9.79 (1H, s) ppm

Example 47

7.61 g of a polymer was prepared in the same manner as in Example 44except that 20 ml of acetone was used as a solvent instead of water, and3.87 g of poly(4-styrenesulfonic acid):

[CH₂CH(C₆H₄SO₃H)—]_(n)

(MW: 70,000) and 3.90 g (23.2 mmol) of1-(1,1,2,2-tetrafluoroethyl)imidazole were used.

According to a NMR analysis, it was confirmed that the obtained productwas poly[1-(1,1,2,2-tetrafluoroethyl)imidazolium 4-styrenesulfonate]having a polymer side chain converted to imidazolium cation (yield:98%).

¹⁹F-NMR (CD₃COCD₃): δ−94.8 (2F), −134.7 (2F) ppm

¹H-NMR (CD₃COCD₃): δ1.40-1.60 (2H), 1.80-2.25 (2H), 6.30-7.10 (5H), 8.12(1H, s), 8.22 (1H), 10.0 (1H) ppm

Example 48

Into a 50 ml two-necked flask were poured 3.19 g (10.2 mmol) of1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium bromide and 20 mlof dichloromethane, and thereto was added dropwise a solution preparedby dissolving 2.08 g (10.7 mmol) of silver tetrafluoroborate in 20 ml ofdichloromethane. After the addition, stirring was continued for one hourin such a state, and then the reaction solution was filtrated withsellaite and the temperature was elevated to 100° C. under reducedpressure, followed by 6-hour drying to obtain 3.10 g of a product(yield: 95%). The obtained product was a highly viscous liquid at roomtemperature.

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium tetrafluoroboratesubjected to anion exchange of bromine with tetrafluoroboric acid.

¹⁹F-NMR (CD₃COCD₃): δ−77.0 (3F), −87.8 (1F), −91.2 (1F), −150.0 (4F),−209.8 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.62 (1H, m), 8.09 (1H, s), 8.24 (1H, s), 9.79 (1H,s) ppm

Example 49

Preparation was carried out in the same manner as in Example 48 by using3.19 g (10.2 mmol) of1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium bromide and 2.70 g(10.7 mmol) of silver hexafluorophosphate. Thus 3.70 g of1-methyl-3-(1,1,2,3,3,3-hexafluoropropyl)imidazolium hexafluorophosphatesubjected to anion exchange of bromine with hexafluorophosphoric acidwas prepared (yield: 96%). The obtained product was a highly viscousliquid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−61.6 (6F), −73.6 (3F), −86.9 (1F), −94.6 (1F),−210.3 (1F) ppm

¹H-NMR (CD₃COCD₃): δ6.56 (1H, m), 8.10 (1H, s), 8.26 (1H, s), 9.88 (1H,s) ppm

Example 50

Into a 50 ml two-necked flask were poured 3.19 g (10.2 mmol) of1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium bromide and 20 mlof water, and thereto was added dropwise 3.50 g (12.2 mmol) of lithiumbis(trifluoromethanesulfonyl)imide. Then the temperature inside a systemwas increased to 70° C., followed by 6-hour stirring. After the insidethe system was brought to room temperature, an organic layer wasseparated, followed by extraction with chloroform three times, dryingwith magnesium sulfate, removal of chloroform under reduced pressure,elevation of the inside temperature to 100° C. under reduced pressure,and then 6-hour drying. 4.70 g of a product was obtained (yield: 89%).The obtained product was a liquid at room temperature.

According to a NMR analysis, it was confirmed that this product was1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide subjected to anion exchange ofbromine with bis(trifluoromethanesulfonyl)imidic acid.

¹⁹F-NMR (CD₃COCD₃): δ−73.1 (3F), −79.0 (6F), −87.3 (1F), −93.3 (1F),−209.4 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.26 (3H, s), 6.78 (1H, m), 8.09 (1H, s), 8.25 (1H,s), 9.99 (1H, s) ppm

Example 51

5.32 g of 1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazoliumbis(pentafluoroethanesulfonyl)imide subjected to anion exchange ofbromine with bis(pentafluoromethanesulfonyl)imidic acid was prepared(yield: 85%) in the same manner as in Example 50 by using 3.19 g (10.2mmol) of 1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium bromideexcept that 4.93 g (12.2 mmol) of sodiumbis(pentafluoroethanesulfonyl)imide was used. The obtained product was ahighly viscous liquid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−74.2 (3F), −81.3 (6F), −87.3 (1F), −93.3 (1F),−123.1 (2F), −125.2 (2F), −209.4 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.23 (3H, s), 6.79 (1H, m), 8.10 (1H, s), 8.26 (1H,s), 10.02 (1H, s) ppm

Example 52

5.40 g of 1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazoliumtris(trifluoromethanesulfonyl)methide subjected to anion exchange ofbromine with tris(trifluoromethanesulfonyl)carbon acid was prepared(yield: 82%) in the same manner as in Example 50 by using 3.19 g (10.2mmol) of 1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium bromideexcept that 5.10 g (12.2 mmol) of lithiumtris(trifluoromethanesulfonyl)methide was used. The obtained product wasa highly viscous liquid at room temperature.

¹⁹F-NMR (CD₃COCD₃): δ−73.0 (3F), −78.5 (9F), −87.4 (1F), −91.7 (1F),−210.2 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.20 (3H, s), 6.79 (1H, m), 8.09 (1H, s), 8.24 (1H,s), 9.96 (1H, s) ppm

Example 53

2.47 g of 1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazoliumdicyanamide subjected to anion exchange of bromine with dicyanimidicacid was prepared (yield: 81%) in the same manner as in Example 50 byusing 3.19 (10.2 mmol) of1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium bromide except that1.09 g (12.2 mmol) of sodium dicyanamide was used. The obtained productwas a solid.

¹⁹F-NMR (CD₃COCD₃): δ−74.4 (3F), −89.2 (1F), −94.1 (1F), −209.7 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.19 (3H, s), 6.81 (1H, m), 8.11 (1H, s), 8.23 (1H,s), 10.02 (1H, s) ppm

Example 54

3.55 g of 1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazoliumhexafluoroacetylacetonate subjected to anion exchange of bromine withhexafluoroacetylacetonate was prepared (yield: 79%) in the same manneras in Example 50 by using 3.19 g (10.2 mmol) of1-(1,1,2,3,3,3-hexafluoropropyl)-3-methylimidazolium bromide except that2.61 g (12.2 mmol) of lithium•hexafluoroacetylacetonate was used. Theobtained product was a highly viscous liquid.

¹⁹F-NMR (CD₃COCD₃): δ−73.8 (3F), −77.4 (6F), −86.8 (1F), −92.6 (1F),−209.6 (1F) ppm

¹H-NMR (CD₃COCD₃): δ4.23 (3H, s), 6.40 (1H, s), 6.84 (1H, m), 8.09 (1H,s), 8.24 (1H, s), 9.80 (1H, s) ppm

INDUSTRIAL APPLICABILITY

According to the preparation process of the present invention, a N—Hgroup of a heteroaromatic ring compound can be converted directly to aN—Rf group at a high reaction yield without using a catalyst. Inaddition, according to this preparation process, many kinds of novelfluorine-containing compounds can be easily synthesized, and as aresult, a fluorine-containing ionic liquid having a low melting pointand characterized by easily compatibilizing a polar compound in a matrixsuch as a fluorine-containing solvent or a fluorine-containing resin canbe obtained.

1-22. (canceled)
 23. A fluorine-containing imidazone compoundrepresented by the structural formula (C-1):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them, Rf^(c1) is afluoroalkyl group represented by the formula (c):

wherein R^(c1), R^(c2) and R^(c3) are the same or different and each isH, halogen atom, a functional group or a monovalent organic group whichmay be substituted by halogen atom, may have an ether bond and may havea polymerizable group, and at least one of R^(c1), R^(c2) and R^(c3) hasat least one polymerizable group at its end, or a monovalent organicgroup which may have at least one residue defined by deleting Rf^(c1)group from the formula (C-1); R^(c1) is not —CFHCF₃, —CF₂CFZ¹H and—CF═CFZ¹ (Z¹ is F or Cl).
 24. The compound of any of claim 23, whereinat least one of R^(c1), R^(c2) and R^(c3) in said formula (c) has theformula (b-1):—(CF₂)_(m1)— wherein m1 is an integer of 1 to 10,000, the formula (b-2):

wherein m2 is an integer of 1 to 10,000, the formula (b-3):(CF₂—CH₂)_(m3)— wherein m3 is an integer of 1 to 10,000, the formula(b-4):

wherein m4 is an integer of 1 to 3,000, and/or the formula (b-5):—(Rf^(b)O)_(m5)— wherein Rf^(b) is a linear or branched alkylene grouphaving fluorine atom; m5 is an integer of 1 to
 100. 25. The compound ofclaim 23, wherein said polymerizable end group is a carbon-carbon doublebond.
 26. A salt of fluorine-containing imidazole compound representedby the structural formula (E-1):

wherein R^(a)s are the same or different, and each is halogen atom, afunctional group or an organic group and may be present or may not bepresent, and when R^(a)s are present, the whole or a part of hydrogenatoms of the heteroaromatic ring are substituted by them; R^(c1) is afluoroalkyl group represented by the formula (c):

wherein R^(c1), R^(c2) and R^(c3) are the same or different and each isH, halogen atom, a functional group or a monovalent organic group whichmay be substituted by halogen atom, may have an ether bond and may havea polymerizable group, or a monovalent organic group which may have atleast one residue defined by deleting Rf^(c1) group from the formula(C-1); R^(c1) is not —CFHCF₃, —CF₂CFZ¹H and —CF═CFZ¹ (Z¹ is F or Cl);R^(c1) is H or a monovalent organic group; X is a counter anion.
 27. Thesalt of fluorine-containing imidazole compound of claim 26, wherein atleast one of R^(c1), R^(c2) and R^(c3) in said formula (c) has theformula (b-1):—(CF₂)_(m1)— wherein m1 is an integer of 1 to 10,000, the formula (b-2):

wherein m2 is an integer of 1 to 10,000, the formula (b-3):—(CF₂—CH₂)_(m3)— wherein m3 is an integer of 1 to 10,000 the formula(b-4):

wherein m4 is an integer of 1 to 3,000, and/or the formula (b-5):—(Rf^(b)O)_(m5)— wherein Rf^(b) is a linear or branched alkylene grouphaving fluorine atom; m5 is an integer of 1 to
 100. 28. The salt offluorine-containing imidazole compound of claim 26, wherein at least oneof R^(c1), R^(c2) and R^(c3) in said formula (c) has at least onepolymerizable group at its end.
 29. The salt of fluorine-containingimidazole compound of claim 28, wherein said polymerizable end group isa carbon-carbon double bond.